Treatment of textile materials

ABSTRACT

Fibrous materials (e.g., wool, cotton, viscose, etc.) carrying a deposit of a preformed polymer containing functional groups, which is cross-linked in situ through reaction with a fixative containing functional groups complementary to those on the polymer. Typically, the functional groups on the polymer are carbonyl halide, haloformate, isocyanate, anhydride, or carbamyl halide groups. In such case, the functional groups on the fixative may be amino or hydroxyl groups. Alternatively, the polymer may contain amino or hydroxyl groups, in which case the fixative would contain carbonyl halide, haloformate, isocyanate, anhydride, or carbamyl groups. Various types of polymers may be employed including addition polymers and copolymers, and condensation polymers such as polyesters, polyamides, and polyethers. The novel products are made by processes which utilize a phase boundary limited reaction. One embodiment thereof is to form the complementary agents (the preformed polymer and fixative) into separate solutions in mutually immiscible solvents, these solutions then being applied serially to the fibrous material. Alternatively, a solution of one of the agents in a volatile solvent is applied to the substrate, which is then dried to remove solvent, and the complementary agent is then applied in fluid form, e.g., as a vapor or dissolved in a solvent which is not necessarily immiscible with the first solvent.

United States Patent [72] Inventors Robert E. Whitfield Pleasant Hill;Allen G. Pittman, El Cerrito; William L. Wasley, Berkeley, all of Calif.

[21] Appl. No. 805,379

[22] Filed Mar. 7, 1969 [45] Patented Jan. 4, 1972 [73] Assignee TheUnited States of America as represented by the Secretary of AgricultureOriginal application May 12, 1967, Ser. No. 655,695, now Patent No.3,440,002, which is a division of application Ser. No. 371,150, May 28,1964, now Patent No. 3,372,978. Divided and this application Mar. 7,1969, Ser. No. 805,379

[54] TREATMENT OF TEXTILE MATERIALS 28 Claims, No Drawings [52] U.S.Cl117/62.2, 117/126 AB, 1 17/126GB, 117/138.8 F, ll7/138.8

UA, 1 17/1388 E, 117/1388 N, 117/1388 D,

[51] lnt.Cl B44d1/44 [50] FieldofSearch 117/621, 62.2, 141,142,143A,148, 155 R, 155 UA, 145,

126 GB, 126 AB, 138.8 F, 138.8 UA, 138.8 E,

138.8 N, 138.8 D, 140 A, 161 P, 161 K, 1

[56] References Cited UNITED STATES PATENTS 3,152,920 10/1964 Caldwellet al. ll7/62.2 X 3,156,579 11/1964 Baldwin et a1. ll7/62.2

3,233,962 2/1966 Nelson 1 17/622 X 3,318,727 5/1967 Boenig 117/622 XFOREIGN PATENTS 957,564 2/1957 Germany Primary Examiner-William D.Martin Assistant Examiner-David Cohen An0rneysR. Hoffman, W. Bier and W.Takacs ABSTRACT: Fibrous materials (e.g., wool, cotton, viscose, etc.)carrying a deposit of a preformed polymer containing functional groups,which is cross-linked in situ through reaction with a fixativecontaining functional groups complementary to those on the polymer.Typically, the functional groups on the polymer are carbonyl halide,haloformate, isocyanate, anhydride, or carbamyl halide groups. In suchcase, the functional groups on the fixative may be amino or hydroxylgroups. Alternatively, the polymer may contain amino or hydroxyl groups,in which case the fixative would contain carbonyl halide, haloformate,isocyanate, anhydride, or carbamyl groups. Various types of polymers maybe employed including addition polymers and copolymers, and condensationpolymers such as polyesters, polyamides, and polyethers. The novelproducts are made by processes which utilize a phase boundary limitedreaction. One embodiment thereof is to form the complementary agents(the preformed polymer and fixative) into separate solutions in mutuallyimmiscible solvents, these solutions then being applied serially to thefibrous material. Alternatively, a solution of one of the agents in avolatile sol vent is applied to the substrate, which is then dried toremove solvent, and the complementary agent is then applied in fluidform, e.g., as a vapor or dissolved in a solvent which is notnecessarily immiscible with the first solvent.

TREATMENT OF TEXTILE MATERIALS This application is a division of ourapplication Ser. No. 655,695, filed May l2, 1967, now U.S. Pat. No.3,440,002, which in turn is a division of our application Ser. No.371,150, filed May 28, 1964, now U.S. Patent No. 3,372,978.

A nonexclusive, irrevocable, royalty-free license in the inventionherein described, throughout the World for all purposes of the UnitedStates Government, with the power to grant sublicenses for suchpurposes, is hereby granted to the Goy e r nent of the United States ofAmerica.

A principal object of this invention is the provision of new methods fortreating fibrous materials, particularly textiles. Another object of theinvention is the provision of the novel products so produced. Furtherobjects and advantages of the invention will be obvious from thefollowing description wherein parts and percentages are by weight unlessotherwise specified. The symbol is used throughout to designate thestructure.

In the processing of fibrous materials, e.g., textiles, it is oftendesired to modify the inherent properties of the materials, for example,to improve their shrinkage characteristics, to increase their resistanceto soiling, to enhance their softness, etc. Various procedures have beenadvocated for such purposes and they usually involve applying to thefibrous substrate an agent having the chemical structure required to effeet the desired modification of the fibers. Such agentswhich may begenerically termed fiber-modifying agents-are generally polymers of anyof various classes, for example, polyethylene, polypropylene, or otherpolyolefines, chlorosulphonated polyethylenes; polyvinylpyrrolidones;polyepoxides; formaldehyde-melamine resins; vinyl polymers; starch andstarch derivatives, etc. Ordinarily, application of the polymer withnothing more yields at best a temporary affeet; the polymer is removedwhen the treated fibers are subjected to laundering or dry cleaning. Toattain a more lasting effect, it is conventional to apply the polymer inconjunction with an agentcommonly termed a fixative or curing agentinorder to cause a cross-linking of the molecules of the polymer renderingit insoluble in water and drycleaning solvents. A universal feature ofsuch procedures is that they require a curing operation at elevatedtemperatures to attain the desired insolubilization of the polymer. Atypical procedure of this type is disclosed by Bruner et al. (US. Pat.No. 2,678,286) who apply a solution containing (a) chlorosulphonatedpolyethylene and (b) a fixative such as hexamethylenediamine or3-methoxyhexamethylene diamine to wool and then cure the treated wool at150 C. for anywhere from 2 to minutes. Such heat curing steps entailserious disadvantages. For one thing, they impede production by tying uplarge amounts of material. For example, in textile mills processing isconducted at rates of at least 25 yards per minute and it is obviousthat if a heat cure of 10 minutes is required, 250 yards of materialwill constantly be tied up in the curing oven, hence not available foruse or sale. Other disadvantages are the expense of the heatingequipment, maintenance of the auxiliary devices such as guides, rollers,etc., and the cost of fuel. A further point is that heating at curingtemperatures often is detrimental to the fibrous material, causing suchdeleterious changes as yellowing, loss in tensile strength and abrasionresistance, and other changes attributable to degradation of the fibermolecules. Wool is a typical example ofa fiber which is readily yellowedand degraded by ex posure to elevated temperatures, particularly when incontact with alkaline substances, e.g., curing agents containing aminogroups.

A particular feature of the present invention is that essentiallypermanent modifications of fiber properties are attained without anyheat-curing step. As a result, the invention yields the advantages ofrapid and simple operation, decreased cost of production, and avoidanceof fiber yellowing and degradation.

In accordance with the invention, the properties of a fibrous substrateare modified by applying thereto a preformed polymer and cross-linkingit to form a three-dimensional structure, the cross-linking beingaccomplished by reaction of the preformed polymer and the fixative at aphase boundary. In a typical embodiment of the invention, wool is firstimpregnated with an aqueous solution of the fixative, e.g., a diaminesuch as hexamethylene diamine. The wool is then impregnated with asolution of a preformed polymer in a waterimmiscible solvent such ascarbon tetrachloride. The polymer may be, for example, a copolymer ofethylene and methacryloyl chloride, containing at least three COClgroups per molecule. By serial application of these solutions to thefabric, each fibrous element is coated with a two-phase system, forexample, an inner layer of diamine in water and an outer layer of thehighly reactive polymer in water-immiscible solvent. Under theseconditions, the diamine and the polymer react almost instantaneously atthe boundary between the phases, producing in situ on the fiber across-linked, insoluble, resin coating. By suitable selection of thecomplementary reactants, a wide variety of polymeric, fiber-modifyingagents can be cross-linked in situ on fibers. It is to be particularlynoted that no heat-curing step is neededthe serial application of thereactants is all that is necessary. The critical feature in this regardis that we provide a phase boundarylimitcd system whereby thecross-linking takes place directlyas soon as the reactants areappliedand hence there is no need for heat curing to promote thereaction.

In the patents of Miller et al. 3,078,138 and Whitfield et al.3,079,216, 3,079,217, 3,084,0l8 3,084,019 and 3,093,44l there aredisclosed processes wherein linear condensation polymerse.g.,polymides-are formed in situ on fibrous substrates by polymerizingcomplementary bifunctional polymer intermediates in an interfacialsystem. Thus in a typical embodiment thereof, wool is first impregnatedwith an aqueous solution of a diamine and then impregnated with asolution of a diacid chloride in a water-immiscible solvent such ascarbon tetrachloride. Under these conditions, polymerization takes placeat the interface between the mutually immiscible phases, producing insitu a linear polyamide.

Although the procedures of the aforesaid patents provide very useful andpractical results and are indeed in commercial use, they inherentlypossess certain limitations. The procedure of the present invention doesnot have these limitations and, moreover, provides results are notobtainable by the prior techniques. These points are further explainedas follows:

1. A fundamental item is that the patented procedure utilizes aninterfacial system to build a polymer from small units so that theprocedure may accurately be termed interfacial polymerization and is soreferred to hereinafter. On the other hand, the present procedure startswith a preformed polymer and utilizes an interfacial system tocross-link it. Thus, the present procedure may be considered'asinvolving interfacial cross-linking of a preformed polymer. Thedistinction is not just a matter of words but involves basic andimportant distinctions. A vital point is that the patented system formslinear polymers. Bifunctional polymer-forming monomers are applied and alinear polymer is produced on the surface of the substrate. In contrast,in the present procedure a preformed linear polymer is initially appliedas the primary reactant. The reaction which then occurs at the phaseboundary is a crosslinking of this preformed polymer; that is,individual molecules of the original polymer arejoined to another,forming a three-dimensional structure.

These distinctions are further demonstrated by the followingillustrative formulas:

(a) interfacial polymerization:

Hex Sab a Hax Bab Hex Seb Hex Seb Hex Snb anahexamethylene aabacoyl.Linea: polyma: containing diamine chloride alternating unite derivedfrom hnxmethyleue diamine and lebaeoyl chloride Preformed line-rpoly-net oi ethylene and uthacryl y]. chloride Hertz-methylene dlmtue (8ethylene unit, M I

mthactyloyl chloride unit) \L yields wwnnwn a s 0 WmmEBEEEHHex-WEEEEMEEEEE H- s n WZMEBEEEEEEBEEE u...

crane-linked (In-linenltnnll) structure containing polymer chains oiethylene and mthactyloyl. units,

linked through hexamethylene amine units Since linear polymers containindependent chains, whereas cross-linked polymers contain interconnectedchains, substantial distinctions in properties are displayed by the twoforms of polymers. For example, linear polymers are soluble in organicsolvents; they are fusible and display typical thermoplastic properties,i.e., they flow when heated. Cross-linked (thermosetting) polymers areinsoluble in organic solvents and at most are swelled thereby. Also,they are not fusible and do not exhibit plastic properties when heated,i.e., they do not flow.

2. The interfacial polymerization system is limited to the formation ofcondensation polymers, i.e., polyamides, polyurethanes, polyureas,polyesters, polycarbonates, and interpolymers containing variouscombinations of amide, urethane, urea, ester, or carbonate groups. incontrast, the procedure of the present invention is not so limited. Onecan apply all kinds of polymersnot only condensation polymers but alsoaddition polymersv As a matter of fact, the present invention is ofparticular advantage for the very reason that one can apply additionpolymers, for example, polyolefines, polyacrylates,polyperfluoroacrylates, polyvinyls, and the like. Addition polymers havethe benefits that they are readily available, relatively inexpensive,and, most importantly, offer a very wide spectrum of physical andchemical properties for the modification of the fibrous substrate. Thislast item is illustrated by the following examples: Application ofelastomers such as chlorosulphonated polyethylene to confer suchattributes as enhanced resiliency; polystyrene polymers to conferstiffness; perfluoracrylates to provide resistance to soiling; etc. Itis important to note at this point that addition polymers cannot beformed by the aforesaid interfacial polymerization technique; monomersrequired to form addition polymers will not polymerize under theconditions in question at any practical rate.

3. In the interfacial polymerization system, permanency of fibermodification is attained only if the polymer becomes grafted to thefiber molecules. 1f the characteristics of the substrate are such thatno grafting occurs, the polymer deposit is but temporary and is removedby such influences as laundering, dry-cleaning, mild abrasion, etc.However, in the process of the present invention grafting is not anessential factor. Pen manence of modification depends on the fact thatthe applied polymer is cross-linked (by reaction with the fixative) toform a polymer which is three-dimensional, hence inherently insoluble.Moreover, if grafting does occur, one attains a double-anchoring effectin that both the grafting and the crosslinking contribute to thepermanence of the fiber modification. To sum up the situation, graftingis essential in the prior procedure where permanence of modification isrequired. In accordance with the present invention, permanence of fibermodification is attained by cross-linking a preformed polymer. Grafting,if it does occur, serves to reinforce the durability of themodification.

4. Another item is that the interfacial polymerization procedure by itsvery nature yields polymers wherein polar groups (amide, urea, urethane,ester or carbonate groups) recur along the polymer chain in relativelyclose spacing. For example, polyhexamethylcne sebacamide (produced bypolymerizing hexamethylene diamine and sebacoyl chloride in situ on afibrous substrate) will contain an amide group recurring after eachgroup of six or eight carbon atoms. Such polarity may be undesirable,for example, in instances where it is intended that the treated fibersdisplay a high degree of hydrophobicity. On the contrary, the process ofthe present invention does not necessarily yield such highly polarproducts and, in fact, one can readily form cross-linked polymers whichcontain very lengthy chains completely free from polar radicals.Typically, this can be done by applying a polymer containing longhydrocarbon chains such as those of polyethylene, polypropylene,polybutylene, etc. The resulting cross-linked polymer will contain verylong carbon chains between polar groups; indeed, these carbon chains maycon tain anywhere from 25 or 50 to hundreds of carbon atoms.

COMPONENT A (THE. PREFORMED POLYMER) in the practice of the invention,selection is made of the appropriate complementary agents to provide thedesired modification of the fibers. These complementary agents willcomprise a preformed polymer (hereinafter termed component A) and thefixative or cross-linking agent (hereinafter termed component B).

As'noted hereinabove, the invention is of wide versatility and amultitude of different substances may be used as component A. Basically,component A may be any polymer which contains highly reactive groups andwhich is soluble in water or in organic solvents such as alcohol,acetone, hydrocarbons, or chlorinated hydrocarbons, etc. From astructural viewpoint, component A is a linear polymer, with or withoutbranching, which possesses the above critical characteristics. It ispreferred that component A have a molecular weight of at least lOOO toprovide adequate film-forming and fiber-modify ing abilityv Thecharacteristic of solubility is desired so that the polymer can beuniformly applied to fibrous substrates in the form of a solution. Thehighly reactive groups are required to provide the sites for theeventual cross-linking of component A in the phase boundary system. Theexpression highly reactive group is employed herein to designate afunctional radical which on contact with a complementary functionalradical under interfacial conditions will combine therewith rapidly anddirectly without requiring any aftertreatments such as oven cures.Because of the facility with which these groups react on contact, theymay also be termed contact-responsive or contact-effective functionalgroups. It is essential that there be at least two, preferably at leastthree, of these highly reactive groups per polymer molecule. For bestresults it is preferred that the number of highly reactive groups becorrelated with molecular weight of the polymer, employing a greaternumber as the polymer molecular weight is increased. Illustrativeexamples of highly reactive groups which may be present are carbonylhalide (-COX); sulphonyl halide so,x haloformatc (-OCOX); carbamylhalide (NH imine (g); and hydroxy (OH). In the above formulas Xmfluorine, chlorine, bromine, or iodine. The sulphur analogues of any ofthe above oxygen-containing species, e.g., CSC1, SCOCl, SCSC1, OCSC1,-NCS, SH, etc., are also included within the ambit of the invention. Theseveral highly reactive groups of component A may be all the same or maybe of different species. For example, the reactive groups may be two ormore carbonyl chloride groups; two or more sulphonyl chloride groups;two or more amine groups; one carbonyl chloride group and one or moresulphonyl chloride groups; one amino group and one or more hydroxylgroups; one chloroforrnate group and one or more carbonyl chloridegroups; etc. Other combinations of two or more different species ofreactive groups will be evident from the above.

The expression acid halide group" is used herein as generic to carbonylhalide, sulphonyl halide, haloformate, and carbamyl halide groups.

Illustrative types of polymers which may be employed as component A aregiven below:

COMPONENT A (ADDITION POLYMERS) Basically, this embodiment of componentA may be considered as an addition polymer which contains pendant highlyreactive groups of the types described above. Typically, thesesubstances are prepared by copolymerizing two types of unsaturatedmonomeric materials, namely, a first ingredient used in major proportion(e.g., about 55 to 95 mole percent of the copolymerization system) and asecond ingredient used in minor proportion (about 5 to 45 mole percentof the copolymerization system). Generally, the first ingredient isprovided to contribute to the copolymer the desired high molecularweight and also to contribute to the polymer the ultimate propertiesdesired to be imparted to the fibrous sub strate in the cross-linkingprocedure, The second ingredient provides the pendant, highly reactivegroups.

Typical examples of monomers which may be used as the major ingredientare:

Alkyl esters of acrylic acid and alkyl esters of any of the variousa-alkylacrylic or a-haloacrylic acids, e.g., the methyl, ethyl, propyl,isopropyl, butyl, amyl, hexyl, octyl, decyl, dodecyl, tetradecyl,hexadecyl, octadecyl, cyclohexyl, oleyl, etc., esters of acrylic,methacrylic, ethacrylic, propacrylic, chloracrylic, bromoacrylic, etc.,acids.

Aryl and aralkyl esters of acrylic acid or the tit-substituted acrylicacids, e.g., phenyl, m-, p-tolyl, dodecylphenyl, benzyl, phenylethyl,etc., esters of acrylic, methacrylic, ethacrylic, propacrylic,chloroacrylic, bromoacrylic, etc., acids.

Alkyl acrylates or methacrylates containing an oxygen bridge, typicallymethoxyethyl acrylate, ethoxyethyl acrylate, propoxyethyl acrylate,butoxyethyl acrylate, octoxyethyl acrylate, cyclohexoxyethyl acrylate,benzoxyethyl acrylate, phenoxyethyl acrylate, methoxyethyl methacrylate,phenoxyethyl methacrylate, etc,

Acrylates containing such radicals as thioether, sulphone, orsulphoxide, for example, the esters of acrylic acid or methacrylic acidwith alcohols of the types:

wherein R is an alkyl radical such as methyl, ethyl, propyl, butyl,etc., or an aryl or aralkyl radical such as phenyl, tolyl, benzyl,phenylethyl, etc.

Vinyl esters of fatty acids, e.g., vinyl acetate, propionate, butyrate,valerate, caprylate, caprate, laurate, myristate, palrnitate, stearate,oleate, etc.

Allyl and methallyl esters of fatty acids, e.g., allyl and methallylacetates, propionates, butyrates, valerates, caprylates, caprates,laurates, myristates, palmitates, stearates, oleates, etc.

N-Dialkyl acrylamides and N-dialkyl a-substituted acrylamides, forexample, N-dimethyl, N-diethyl N-dipropyl, N- dibutyl, N-diamyl,N-dihexyl, N-dioctyl, N-didodecyl, etc., acrylamides, methacrylamides,ethacrylamides, propacrylamides, etc.

Olefinic hydrocarbons and halogenated olefinic hydrocarbons such asethylene, propylene, butylene, isoprene, butadiene, styrene,chloroprene, a-methylstyrene, dimethylstyrene, vinyl naphthalene,dichlorostyrenes, vinyl chloride, vinyl bromide, vinylidene chloride,vinylidene bromide, vinyl fluoride,etc.

Ketones such as methyl vinyl ketone, ethyl vinyl ketone, isopropyl vinylketone and other alkyl vinyl ketones, methyl isopropyl ketone, methylalkyl ketone, etc.

ltaconic diesters, for example, the dimethyl, diethyl diisopropyl,dibutyl, dihexyl, didodecyl, and other dialkyl esters of itaconic acids.Diaryl and diaralkyl esters of itaconic acid, e.g., diphenyl itaconate,dibenzyl itaconate, di-(phenylethyl) itaconate, etc.

Other compounds containing the typical grouping such as cyanostyrenes,vinyl thiophene, vinyl pyridine, vinyl pyrrole, acrylonitrile,methacrylonitrile, alkyl vinyl sulphones such as ethyl vinyl sulphone.Compounds of the types:

where R is H or CH and wherein R is a lower alkyl group such as Ch C Hetc.

Vinyl ethers, for example, monomers of the type CH CH O-R wherein R isan alkyl radical such as methyl, ethyl, propyl, butyl, benzyl, etc.

In many cases, it is preferred that the major ingredient be afluorine-containing monomer. Copolymers produced therefrom are useful toimpart such characteristics to the fibrous substrates as resistance toboth oiland water-borne soils. Typical illustrative examples offluorine-containing monomers are: perfluoro-t-buytl acrylate,perfluoro-t-butyl methacrylate, and esters of the type wherein R is H orCH;, and n is an integer from 2 to 6. Typical examples of this type ofprimary perfluoralkyl ester are: l, l ,5- trihydroperfluoropentylacrylate and methacrylate, l,l,7- trihydroperfluoroheptyl acrylate andmethacrylate, l,l,9- trihydroperfluorononyl acrylate and methacrylate,l,l,l ltrihydroperfluoroundecyl acrylate and methacrylate, l,l,l3-trihydroperfluorotridecyl acrylate and methacrylate, etc. Usually, it ispreferred that the fluoroalkyl radical contain at least 3 fluorine atomsand an especially desirable type of fluoroalkyl ester for themultipurpose treatment mentioned above is one wherein the fluoroalkylradical not only contains at least three fluorine atoms but also has itsomega carbon atom completely fluorinated. Typical of these particularlypreferred fluoroalkyl esters are those of the type i CF;-(CF;),,CH1O--C=CH1 o,

wherein R is H or CH and n is an integer of from to l8. Illustrativeexamples of such compounds are the acrylic and 5 CIIQ=C'S 02Xmethacrylic acid esters of: l,l-dihydroperfluoropropyl a]- cohoi,l,l-dihydroperfluorobutyl alcohol, l,l-dihydroperwherein RandXare asdefinedinUW fluorohexyl alcohol, 1,1-dihydroperfluorooctyl alcohol, l,l-3. Unsaturated monomers containing carboxylic acid ordihydroperfluorodecyl alcohol, l,l-dihydroperfluorododecyl sulphonicacid groups, for example alcohol, 1,1 -dihydroperfluorohexadecylalcohol, l,ldihydroperfluorooctadecyl alcohol, etc.

Another useful type of fluorine-containing monomer com- CHz=C- 00Mprises the compounds of the structure R 1?. E") I? I5 0H,=( Js 0,,M

R!S0 .NC-C=CH2 Ii wherein R, is a saturated fluorocarbon structurecontaining GHFO 000M from four to 18 fully fluorinated carbon atoms, Ris hydrogen or an alkyl group containing from one to six carbon atomsand 20 0H1=Cs 0 M R" is hydrogen or a methyl group. Typical examples ofpar- I ticular compounds in this area are: N-methyl,N-perfluorobuwherein R is as defined in l above and wherein M is H or antanesulfonyl acrylamide; N-methyl, N-pert'luorobutanesulfoalkali metal.nyl methacrylamide; N-perfluoro(Z-methylcyclohexane)sulfo- Copolymersmade with these sulphonicor carboxylic-connyl methacrylamide; N-methyl,N-perfluoroM-methyltaining monomers may be converted to thecorresponding cyclohexane)sulfonyl acrylamide; N-propyl, N-perfluoro(2-acid halide forms by, for example, reaction with a thionylhamethylcyclohexane)sulfonyi methacrylamide; N-perfluorooclide,phosphorus trichloride, or the like. tanesulfonyl acrylamide;N-perfluorooctanesulfonyl 4. Unsaturated monomers containing anisocyanate or methacrylamide; N-ethyl, N-perfluorooctanesulfonylacrylaisothiocyanate group, for example, compounds of the types mide;N-isobutyl, N-perfluoro(4-ethylcyclohexane)-sulfonyl acrylamide;N-isobutyl, N-perfluorodecanesulfonyl methacrylamide; N-propyl,N-perfluorododecanesulfonyl CHz=C-NGY acrylamide', N-(n-hexyl),N-perfluorooctadecanesulfonyl R acrylamide.

In cases where it is desired to impart water repellency to the CH1=CCH2NCY fibrous substrate, one may employ as the major ingredient un- R 0saturated monomers containing silicon. Typical in this categoll Y ry arethe acryloxyrnethyl (or methacryloxymethyl) deriva- CH C C O R NC tivesof organic silanes or polysiioxanes, for example, comf pounds of thetypes 40 CH =C-N CY wherein R is as defined in (l) above, R is abivalent radicai RSi-CHOCC=CH; such as ethylene or other alkyleneradical or a phenylene group etc., and Y is O or S. 5. Unsaturatedmonomers containing an anhydride or imide i q group as, for example,maleic anhydride or imide, itaconic anhydride or imide, etc.

6. Unsaturated monomers containing free amino groups or r hydroxylgroups, for exampie, compounds of the types wherein R is hydrogen ormethyl and the Rs are monovalent R organic radicals, typically alkylgroups containing one to 18 carbon atoms, cyclohexyl, phenyl, toluyl,benzyl, diphenyl, or CHFCGHZOH the like. Typical examples of compoundsin this category are R acryloxymethyl trimethylsilane,methacryloxymethyl trimethylsilane, acryloxymethyl dimethylphenylsilane,methacryloxymethyl dimethyiphenylsilane, acryioxymethylpentamethyldisiloxane, methacryloxymethyl pentamethyldis- CH g O RI OHiloxane, etc.

illustrative examples of the minor ingredient are as follows: f l.Unsaturated monomers containing a carbonyl halide CH;==C-CORNHR group,e.g., compounds of the formula R l CH -C- NHR wherein R is hydrogen, analkyl group such as methyl, ethyl, 2- propyl, butyl, phenyl, etc., andwherein X is Cl, Br, F or I. wherein R is as defined in i above and R isas defined in (4) Styrene derivatives of the type above. V n i 7.Unsaturated monomers containing a haloformate or car- R bamyl halidegroup, for example CH t J--C 0X 1? wherein X and R are as defined aboveCHFC CH O C 0X 2. Unsaturated monomers containing a sulphonyl halide Ifgroup. e.g., compounds of the formulas C1I2=Cn-NIICOX V 7 77 wherein Rand X are as defined in (1) above and wherein R is as defined in (4)above.

COMPONENT A (CONVERTED ADDITION POLYMERS) if desired, one may prepareaddition polymers essentially free from highly reactive groups and thensubject them to known reactions to introduce the necessary highlyreactive groups. An example in this area is the chlorosulphonation ofpolyoflefines such as polyethylene or polypropylene by reaction with Sand C1 This introduces chloro groups and sulphonyl chloride (SO Cl)groups into the polymer. Another example is the partial hydrolysis ofvinyl ester or vinyl ether polymers, to introduce hydroxyl groups intothe polymer chain. Another example is a copolymer containing carboxygroups which are then converted into carbonyl halide groups by reactingthe copolymer with such agents as thionyl chloride, phosphorustrichloride, or the like.

COMPONENT A (CONDENSATION POLYMERS) Component A need not necessarily bean addition polymer;

one may use condensation polymers of all types. Although someinvestigators employ the term condensation polymer only in respect topolymers wherein a low molecular weight byproduct (such as H O or l-iCl)is split out during polymer formation, we employ the term in the broaderand accepted sense as designating any polymer which contains interunitfunctional groups not present in the monomers. Thus, we include suchtypes as polyalkyleneimines, polyurethanes, polyureas, etc., whoseformation is not ordinarily accompanied by any byproduct elimination.Various types of condensation polymers which may be used in the practiceof the invention are listed in the following paragraphs by way ofillustration but not limitation.

COMPONENT A (POLYALKY LENE IMINES) A useful class of polymers which canbe used as component A are the polyalkylene imines. A special feature ofthese is that they have built-in reactive groups on the polymerbackbone, namely, internal imine (NH-groups and terminal amine (NHgroups. Typical examples are the polymers of ethylene imine, propyleneimine, 1,2-butylene imine, 2,3-butylene imine, 2,2-dimethyl ethyleneimine, 2,2,3- trimethyl ethylene imine, 2,2-dimethyl-3-propyl ethyleneimine, cyclohexyl ethylene imine, phenyl ethylene imine, etc. Thesecompounds, as well known in the art, can be prepared, for example, bypolymerizing the alkylene imine monomer in the presence of a catalystsuch as sodium bisulphite, hydrochloric acid, sulphuric acid, aceticacid, hydrogen peroxide, etc. Generally, it is preferred to use thepolyalkylene imines which are at least partially soluble in water.

COMPONENT A (POLYESTERS) Polyesters derived from polyols such asethylene glycol, propylene glycol, trimethylene glycol, hexamethyleneglycol, glycerol, pentaerythritol, sorbitol, trimethylolpropane, etc.,and dibasic acids such as succinic, adipic, sebacic, phthalic,

terephthalic, hexahydrophthalic, maleic, and the like. By suitableadjustment of the proportions of reactants in known manner, thepolyesters will contain free hydroxy groups. The resulting polyesterscan be employed directly as component A, utilizing the free hydroxygroups as the highly reactive groups. Another plan is to react thehydroxylated polyethers with a diacid chloride (or bischloroformate) toprovide a polyether containing free carbonyl chloride (or chloroform ategroups). In this connection, typical reactants are succinyl chloride,adipyl chloride, pimelyl chloride, sebacyl chloride, phthalyl chloride,ethylene glycol bischloroformate, diethylene glycol bischloroformate,hexane-l ,6-diol bischloroformate, and the like. As well known in theart, the polyester and diacid chloride (or bischloroformate) are employed in such proportion as to provide a COCl/OH (or OCOCl/OH) ratio ofmore than one to one whereby to ensure that the product contains freecarbonyl chloride or chloroformate groups. In a preferred form of theinvention, one uses polyesters containing free isocyanate groups. Suchpolymers can be readily prepared by reacting the hydroxylated polyesterwith a diisocyanate. Typical examples of the diisocyanates are 0-, M-,or p-phenylene diisocyanate, toluene 2,4- (or 2,6-) diisocyanate,metaxylylene diisocyanate, 3,5,3',5'- bixylylene-4,4'-diisocyanate, etc.As well known in the art, the diisocyanate and polyester are employed insuch proportion as to provide an NCO/OH ratio of more than one to onewhereby to ensure that the product contains free NCO groups. Products ofthis type are sometimes referred to in the art as polyurethanes becausethey contain internal urethane groups, formed through combination ofhydroxy groups of the polyester with isocyanate groups of thediisocyanate reactant.

COMPONENT A (POLYETHERS) Polyethers derived, for example, bypolymerizing an oxide (or epoxide, as they are often termed) with apolyhydric alcohol such as ethylene glycol, propylene glycol,trimethylene glycol, glycerol, pentaerythritol, sorbitol,trimethylolpropane, etc. Generally, the polyethers are derived from thesimple alkylene oxides such as ethylene oxide or propylene oxide but onemay also use such compounds as butylene oxide, isobutylene oxide,trimethylethylene oxide, dodecylene oxide, hexadecylene oxide,tetramethylethylene oxide, a-methylstyrene oxide, styrene oxide,cyclopentene epoxide, cyclohexene epoxide, vinyl cyclohexene epoxide,butadiene monoepoxide, naphthyl ethylene oxide, dipentene epoxide,l,2-epoxy-2,4,4- trimethyl pentane (diisobutylene epoxide),l,l-diphenylethylene oxide, epifluorhydrin, epichlorhydrin,epibromhydrin, l,l,l-trifluoro-Z-propylene oxide, l,l,l-trifluoro-lmethyl-Lpropylene oxide, l,l,l-trifluoro-Z-butene oxide, 1,1, 1,2,2,3,3-heptafluoro-4-hexene oxide, hexylglycidyl ether, allylglycidylether, phenylglycidyl ether, 2-chloroethylglycidyl ether,o-chlorophenylglycidyl ether, methacrylchloride epoxide,3-chloro-l,2-epoxybutane glycidol, methyl 9,10-epoxystearate,3,4-epoxycyclohexyl cyanide, 2-methyl-2,3-epoxyhexanol, etc. Theresulting polyethers can be employed directly as component A, utilizingthe free hydroxy groups as the highly reactive groups, In such case, itis preferred that the polyethers contain at least 3 hydroxy groups permolecule, obtainable by utilizing a polyhydric alcohol containing atleast 3 hydroxy groups in the polymerization with the oxide monomer.Another plan is to react the hydroxylated polyether with a diacidchloride (or bischloroformate) to provide a polyether containing freecarbonyl chloride (or chloroformate groups). in this connection, typicalreactants are succinyl chloride, pimelyl chloride, sebacyl chloride,phthalyl chloride, ethylene glycol bischloroformate, diethylene glycolbischloroformate, hexane-1,6-diol bischloroformate, and the like. Aswell known in the art, the polyether and diacid chloride (orbischloroformate) are employed in such proportions as to furnish aCOCl/OH (or OCOCl/OH) ratio of more than one to one whereby to ensurethat the product contains free carbonyl chloride or chloroformategroups. In a preferred form of the invention, one uses polyetherscontaining free isocyanate groups. Such polymers can be readily preparedby reacting the hydroxylated polyether with a diisocyanate. Typicalexamples of the diisocyanates which may be reacted with the polyethersare m-, or p-phenylene diisocyanates, toluene 2,4- (or 2,6-)diisocyanate, metaxylylene diisocyanate,3,5,3',5-bixylylene-4,4-diisocyanate, 3,3- bitolylene diisocyantate,diphenylmethane-4,4'-diisocyanate, naphthalene-l,S-diisocyanate, etc. Aswell known in the art, the diisocyanate and polyether are employed insuch proportions as to provide an NCO/OH ratio of more than one to onewhereby to ensure that the product contains free isocyanate groups.These products are sometimes referred to as polyurethanes because theycontain internal urethane groups, formed through the combination ofhydroxy groups of the polyether with isocyanate groups of thediisocyanate reactant.

COMPONENT A (POLY AMlDES) The polyamides used in accordance with theinvention are those derived from polyamines and polybasic acids. Methodsof preparing these polyamides by condensation of polyamines andpolycarboxylic acids are well known in the art and need not be describedhere. One may prepare polyamides containing free amino groups or freecarboxylic acid groups. Generally, it is preferred to employ polyamideswhich contain free amino groups. The polyamides may be derived from suchpolyamines as ethylene diamine, diethylene triamine, triethylenetetramine, tetraethylene pentamine, l,4-diamino butane,1,3-diaminobutane, hexamethylene diamine, 3-(N- isopropylamino)propylamine, 3,3-imino-bispropylamine, and the like. Typicalpolycarboxylic acids which may be condensed with the polyamines to formpolyamides are glutaric acid, adipic acid, pimelic acid, suberic acid,azelaic acid, sebacic acid, isophthalic acid, terephthalic acid,betamethyl adipic acid, 1,2-cyclohexane dicarboxylic acid, malonic acid,polymerized fat acids, and the like. Depending on the amine and acidconstituents and conditions of condensation, the polyamides may havemolecular weights varying about from 1,000 to 10,000 and melting pointsabout from -200 C. Particularly preferred for the purpose of theinvention are the polyamides derived from aliphatic polyamines andpolymeric fat acids. Such products are disclosed, for example, by Cowanet al., US. Pat. No. 2,450,940. Typical of these polyamides are thosemade by condensing ethylene diamine or diethylene triamine withpolymeric fat acids produced from the polymerization of drying orsemidrying oils, or the free acids, or simple aliphatic alcohol estersof such acids. The polymeric fat acids may typically be derived fromsuch oils as soybean, linseed, tung, periila, oiticica, cottonseed,corn, tall, sunflower, safflower, and the like. As well known in theart, in the polymerization the unsaturated fat acids combine to producea mixture of dibasic and higher polymeric acids. Usually the mixturecontains a preponderant proportion of dimeric acids with lesser amountsof trimeric and higher polymeric acids, and some residual monomericacid. Particularly preferred are the polyamides of low melting point(about 2090 C.) containing free amino groups which may be produced byheating together an aliphatic polyamine, such as diethylene triamine,triethylene tetramine, 1,4-diaminobutane, tetraethylene pentamine,1,3-diaminobutane, and the like, with the polymerized fat acids. Typicalamong these is a polyamide derived from diethylene triamine anddimerized soybean fatty acids.

COMPONENT A (OTHER CONDENSATlON TYPES) A useful class of condensationpolymers, particularly where it is desired to impart such qualities asshrink resistance, water rcpcllcncy, resistance to water-borne soils,etc., are the polysiloxanes. Typical are the polymers containing amultiplicity of siloxane units of the structure wherein R is amonovalent organic radical such as alkyl containing one to 18 carbonatoms, pheny1,benzyl,toluyl,biphenyl, cyclohexyl, or the like, R is analkylene group containing, for example, two to H) carbon atoms, and Q isOH, NH COCl, NCO or other highly reactive group as disclosed herein.Also typical are copolymers containing a multiplicity of units of thetypes I l sr-o and si-O- R lit wherein R, R, and O are as above. Thepolymers or copolymers may be modified to introduce selected highlyreactive groups. For example, polymers or copolymers containing free OHor NH groups may be reacted with an excess of a diisocyanate, such astoluene diisocyanate, to provide a siloxane with free isocyanate groups.Similarly, polymers or copolymers containing free OH or NH groups may bereacted with an excess of a diacid chloride or a bischloroformate-forexample, adipoyl chloride or ethylene glycol bischlorofor mate-toproduce a siloxane containing free carbonyl chloride or chloroformategroups.

Other class of condensation polymers usable as component A are: polymerscontaining free amine or isocyanate groups prepared by copolymerizing adiamine such as hexamethylene diamine with a diisocyanate such astoluene diisocyanate. Polycarbonates containing free hydroxy orchloroformatc groups, prepared by copolymerizing a polyol such asbisphenol A with ethylene glycol bischloroformate. Po|ycarbonatescontaining free hydroxy groups may be reacted with diisocyanates, asdescribed hereinabove in connection with the polyesters, to provide apolycarbonate containing free isocyanate groups.

COMPONENT B (THE FlXATlVE) Component B may be any compound containing atleast two highly reactive groups. As to these groups, the same choice isavailable as set forth hereinabove in connection with component A andthus they may typically be of the following types: Carbonyl halide(COX), sulphonyl halide (SO X), haloformate (OCOX), carbamyl halide(NHCOX), anhydride amine (NH- imine (NH-), hydroxy (OH), isocyanate(NCO). in the above formulas, X stands for F, Cl, Br, or I. The sulphuranalogues of any of the above oxygencontaining species, e.g., CSCl,SCOCl, SCSCI, OCSCl, NCS, SH, etc., are also included within the am bitof the invention.

The several reactive groups of component B may be all of the samespecies or of different species. For example, the reactive groups may betwo or more carbonyl chloride groups; two or more sulphonyl chloridegroups; two or more amine groups; one carbonyl chloride group and one ormore sulphonyl chloride groups; one amine group and one or more hydroxylgroups; etc. Other combinations of two or more different species ofreactive groups will be evident from the above illustrations.

it is, of course, obvious that in a practice of the invention oneselects components A and B so that they contain reactive groups whichare in a complementary relation, that is, which Complementary ReactiveGroups Reactive group on one component (A or B) Complementary reactivegroup on complementary component (B or A) Carbonyl halide Amine, imine,hydroxy Sulfonyl halide Amine, imine, hydroxy Halofurmate Amine, imine,hydroxy Carbumyl halide Amine, imine, hydroxy Amine, imine, or hydroxyCarbonyl halide, sulfonyl halide, haloformale. carbamyl halide,isocyanate, isothiocyanate. anhydride Amine, imine. or hydroxy Amine,imine, or hydroxy lsocyanate or isothiocyanate Anhydride or imide Wegenerally prefer to employ systems wherein one com ponent carriescarbonyl halide, haloformate, or isocyanate groups and the othercomponent carries groups containing active hydrogen atoms, i.e.,hydroxy, amine, or imine groups. Of these, amine and imine groups areparticularly preferred as providing especially rapid cross-linking.Systems with isocyanates and amines (or imines) offer the specialbenefit that the cross-linking does not produce any byproducts, e.g., nohydrogen halide as in the acid halide-amine systems.

Since the goal of the phase boundary-limited reaction is to cross-linkthe preformed polymer (component A), it is necessary that each of thecomponents A and B contain at least two reactive groups and, moreover,that the sum of the groups be five or more. For example, if the selectedcomponent A contains two of the highly reactive groups, component Bshould contain no less than three of the complementary reactive groups.If the selected component A contains three of the reactive groups, it isevident that component B may contain as few as two of the complementarygroups. MOreover, as the molecular weight of component A is increased,it is preferred that the sum of the reactive groups be more than five toassure the proximity of complementary reactive groups during thecross-linking reaction.

Illustrative examples of compounds which may be used as component B arelisted below:

COMPONENT B (FIXATIVE) CONTAINING COX GROUPS Typically, one may employcompounds of the aliphatic, aromatic, or heterocyclic series containingat least two carbonyl halide (COX) groups. The compounds may besubstituted if desired with noninterfering (nonfunctional) substituentssuch as ether groups, thioether groups, sulphone groups, etc. Typicalexamples of compounds in this category are listed below merely by way ofillustration and not limitation: phosgene, oxalyl chloride, maleylchloride, fumaryl chloride, malonyl chloride, succinyl chloride,glutaryl chloride, adipyl chloride, pimelyl chloride, suberyl chloride,azelayl chloride, sebacyl chloride, cyclohexane-l,4-biscarbonylchloride, phthalyl chloride, isophthalyl chloride, terephthalylchloride, 4,4- biphenyldicarbonyl chloride, B-hydromuconyl chloride,i.e., Cl COCI-I -CH CH-Clh-CO Cl, diglycollic acid chloride, i.e.,O(CI-I CO Cl) higher homologues of this compound as O(CH CH CO Cl)dithiodiglycollic acid chloride, diphenylolpropanediacetic acidchloride, i.e., (CI-I C(C H O CH CO Cl) trimellityl chloride, i.e., CH;,(COCl);,, and the like. If desired, mixtures of different carbonylhalides may be used. It is also evident that the sulphur analogues ofthese compounds may be used and are included within the spirit of theinvention. Thus, instead of using compounds containing two COCl groupsone may use compounds containing one CSCl and one COCl group orcompounds containing two CSCl groups. Moreover, although the carbonylchlorides are preferred as they are reactive and relatively inexpensive,the corresponding fluorides, bromides, and iodides may be used.

It is generally preferred to use the aliphatic compounds containing twocarbonylchloride groups in alpha, omega positions, particularly those ofthe type:

Cl CO(CH ),,CO Cl wherein n has a value from 2 to 12. Another preferredcategory includes the compounds of the formula ClCOACOCl (where A is thebenzene or cyclohexane radical), especially para-substituted compoundssuch as terephthalyl and hexahydroterephthalyl chlorides.

COMPONENT B (FIXATIVE) CONTAINING SO X GROUPS Typically, one may employcompounds of the aliphatic, aromatic, and heterocyclic series containingat least two sulphonyl halide (SO X) groups. The compounds may besubstituted if desired with noninterfering (nonfunctional) groups suchas ether groups, thioether groups, sulphone groups, etc. Typicalcompounds in this category are listed below by way of illustration andnot limitation: benzene-1,3-disulphonyl chloride,benzene-1,4-disulphonyl chloride, naphthalene-L5- disulphonyl chloride,naphthalene-2,7-disulphonyl chloride, biphenyl-4,4disulphonyl chloride,hexane-1,6-disulphonyl chloride, cyclohexane-l ,4-disulphonyl chloride,ethanel ,2- disulphonyl chloride, toluene disulphonyl chloride,p,p'-oxybis (benzenesulphonyl chloride), and compounds of the type XSO(CH ),,SO X wherein X is F, Cl, Br, or I and n has a value from 2 to 12.

COMPONENT B (FIXATIVE) CONTAINING OCOX GROUPS Typically, one may employcompounds of the aliphatic, aromatic, or heterocyclic series containingat least two haloformate (OCOX) groups. The compounds may be substitutedif desired with noninterfering (nonfunctional) substituents such assulphone groups, ether groups, thioether groups, etc. Typical examplesof compounds in this category are listed below merely by way ofillustration and not limitation: ethylene glycol bischloroformate,diethylene glycol bischloroformate, 2,2-dimethyl propane 1,3-diolbischloroformate, propane-1,3-diol bischloroformate, butane-l,4-diolbischloroformate, hexane-1,6-diol bischloroformate, octanel,8-diolbischloroformate, decanel ,lO-diol bischloroformate, butane-1,2-diolbischloroformate, hexane-l ,2-diol bischloroformate, 2-methoxyglyceroll,3-bischloroformate, glycerol-1,2-bischloroformate, glycerol- 1,3-bischloroformate, diglycerol bischloroformate, hexanetriolbischloroformate, pentaerythritol bischloroformate, cyclohexane-l,4-diol bischloroformate, hydroquinone bischloroformate, resorcinolbischloroformate, catechol bischloroformate, bischloroformate of2,2-bis(parahydroxyphenyl) propane, bischloroformate of2,2-bis(parahydroxyphenyl) butane, bischloroformate of4,4-dihydroxybenzophenone, bischloroformate of |,2-bis(parahydroxyphenyl) ethane, naphthalene-l ,S-diol bischloroformate,biphenyl-4,4-diol bischloroformate, glycerol trichloroformate,pentaerythritol tetrachloroformate, and the like. If desired, mixturesof different bishaloformates may be used.

Among the preferred compounds are the aliphatic bischloroformates, forexample, those of the type:

wherein n has a value from 2 to 12. Another preferred category ofcompounds are the bis-chloroformates derived from polyethylene glycols,e.g.,

wherein n has a value from zero to 10. A useful category of aromaticbischloroformates are the bisphenol chloroformates, that is, compoundsof the type:

wherein R-CR represents an aliphatic hydrocarbon group containing one to12 carbon atoms, R is hydrogen or a lower alkyl radical.

It is also evident that the sulphur analogues of the bischloroformatesmay be used and such are included within the spirit of the invention.Thus, instead of using the compounds containing haloformate groups, onemay use any of the compounds containing the sulphur analogues of thesegroups, for example, the compounds containing two or more groups of theformula wherein one Z is sulphur and the other is oxygen or wherein bothZs are sulphur. The symbol X in the above formula stands for a halogen.

COMPONENT B (FIXATIVE) CONTAINING NHCOX GROUPS Aromatic, aliphatic, orheterocyclic compounds containing at least two carbamyl halide (NHCOX)groups. The compounds may be hydrocarbon carbamyl halides or may containnoninterfering (nonfunctional) groups such as ether, thioether,sulphone, etc., groups. Typical compounds in this category are givenbelow by way of illustration and not by way of limitation: ethylenedicarbamyl chloride, trimethylene dicarbamyl chloride, tetramethylenedicarbamyl chloride, hexamethylene dicarbamyl chloride, octamethylenedicarbamyl chloride, Z-methylpropane-l ,Z-dicarbamyl chloride,2,6-dimethyloctane-2,7-dicarbamyl chloride, cyclohexanel,4-dicarbamylchloride, diethyl ether-2,2'-dicarbamyl chloride, diethylthioether-2,2-dicarbamyl chloride, piperazine dicarbamyl chloride, m-,and p-phenylene dicarbamyl chloride, xylylene dicarbamyl chloride, andtheir sulphur analogues, i.e., the corresponding dithiocarbamylchlorides. If desired, mixtures of different dior tricarbamyl halidesmay be used. It is generally preferred to use compounds of the typeXCONH-(CH ),,-NHCOX wherein X is F, Cl, Br, or l and n has a value of 2to I2.

COMPONENT B (FIXATIVE) CONTAINING NH OR NH GROUPS Component B in thiscategory may be any of the aromatic, aliphatic, or heterocycliccompounds containing at least two amine (NH or imine (-NH-) groups. Thecompounds may be hydrocarbon amines or imines or may containnoninterfering (nonfunctional) groups such as ether groups, thioethergroups, sulphone groups, fluorine groups, etc. Typical compounds in thiscategory are listed below by way of illustration but not limitation:ethylene diamine, trimethylene diamine, tetramethylene diamine,hexamethylene diamine, octamethylene diamine, decamethylene diamine,N,N'- dimethyll ,3-propanediamine, l,2-diamino-2-methylpropane,2,7-diumino-2,o-dimethyloctane, N,N'-dimethyl-l ,6-hexancdiamine,l,4-diamino cyclohexane, l,4-bis-(aminomethyl) cyclohcxanc,2,2-diaminodiethyl ether, 2,2'-diaminodiethyl sulphide,bis-(4-aminocyclohexyl) methane, N,N'-dimethyl-2,2,3,3,4,4-hexafluoropentane-l,S-diamine, ortho-,meta-, orpara-phenylene diamine, benzidine, xylylene diamine, m-

toluylene diamine, ortho-tolidine, piperazine, diethylene triamine,triethylene tetramine, tetraethylene pentamine, 3,3 imino-bispropylamine, 6,6'-imino-bishexyl amine, pentaerythrityl amine, and the like.If desired, mixtures of the amines or imines may be used. It isgenerally preferred to use aliphatic alpha, omega diamines, particularlyof the type wherein n has a value of 2 to 12, preferably 6 to l0.

Another preferred class is compounds of the type wherein n is 2, 3, or4.

COMPONENT B (FIXATIVE) CONTAINING OH GROUPS Component B in this categorymay be any of the aromatic, aliphatic, or heterocyclic compoundscontaining at least two hydroxy groups. The compounds may be hydrocarbonpolyols or may contain noninterfering (nonfunctional) radicals such asether groups, thioether groups, sulphone groups, etc. Typical compoundsin this category are listed below by way of illustration but notlimitation: ethylene glycol, diethylene glycol, 2,2-dimethylpropane-1,3-diol, propane-1,3-diol, butane-1,4-diol, hexane-1,6-diol,octane-1,8-diol, demure-1,10- diol, dodecane-l,l2-diol, butane-1,2-diol,hexane-l,2-diol, l- O-methyl glycerol, Z-O-methyl glycerol, cyclohexanel,4-diol, hydroquinone, resorcinol, catechol, bis(parahydroxyphenyl)methane, 1 ,2 bis( parahydroxyphenyl) ethane, 2,2-bis(parahydroxyphenyl) propane, 2,2-bis(parahydroxyphenyl) butane,4,4"dihydroxybenzophenone, naphthalene-1,5- diol, biphenyl-4,4'-diol,2,2-bis(3-methyl-4-hydroxyphenyl) propane,2,2-bis(3-isopropyl-4-hydroxyphenyl) propane, 2,2-bis(4-hydroxy-dibromophenyl) propane, glycerol, diglycerol, hexanetriol,pentaerythritol, etc. Moreover, it is within the spirit of the inventionto utilize the sulphur analogues of the diols. Thus, for example,instead of using the compounds containing two hydroxy groups one can usethe analogues containing either (a) two -SH groups or (b) one -SH groupand one -OH group.

Among the preferred compounds are the aliphatic diols, for example,those of the type:

HO(CH ),,OH wherein n has a value from 2 to 12. Another preferredcategory of aliphatic compounds are the polyethylene glycols, i.e.:

HO-CI-l CH [O-CH CH ],,O-CH -CH 0H wherein n has a value from zero tol0.A preferred category of aromatic diols are the bisphenols, that is,compounds of the type:

1 it R wherein RC-R represents an aliphatic hydrocarbon group containingone to 12 carbon atoms, and R represents hydrogen or a lower alkylradical. In this category especially preferred compounds are2,2-bis(parahydroxyphenyl) propane, often designated as bisphenol-A;2,2-bis(3-methyl-4- hydroxyphenyl) propane;2,2-bis(3-isopropyl-4-hydroxyphenyl) propane; and brominated derivativesof bisphenol A, such as 2,2-bis(4-hydroxy-dibromophenyl) propane.

The hydroxy compounds are employed as such in the phase boundary-limitedcross-linking or in the form of their alkalimetal salts, that is, asalcoholates or phenolates, depending on whether the polyols arealiphatic or aromatic.

COMPONENT B (FIXATIVE) CONTAINING NCO GROUPS Component B in thiscategory may be any of the aliphatic, aromatic, or heterocycliccompounds containing at least two isocyanate (NCO) groups. The compoundsmay be hydrocarbon isocyanates or may contain noninterfering(nonfunctional) radicals such as ether groups, thioether groups,

wherein 2 stands for the radical It is also evident that the sulphuranalogues of these com pounds may be used and such are included withinthe spirit of the invention. Thus for example, instead of using thecompounds containing two NCO groups one may use their analoguescontaining either two NCS groups or one NCO group and one NCS group.

Among the preferred compounds are the aliphatic diisocyanates, forexample, those of the type wherein n has a value from 2 to 12. Otherpreferred compounds are the toluene diisocyanates, xylylenediisocyanates, and diphenylmethane-4,4'-diisocyanate which may also betermed methylene-bis(p-phenylisocyanate).

COMPONENT B (FIXATlVE) CONTAINING ANHYDRIDE OR lMlDE GROUPS Component Bin this category may be any of the aliphatic, aromatic, or heterocycliccompounds containing at least two anyhydride or imide groups. Thecompounds may be hydrocarbon anhydrides or imides or may containnoninterfering (nonfunctional) radicals such as ether groups, thioethergroups, sulphone groups, tertiary amine groups, etc. Typicalillustrative examples in this category are: 3,31,41,4- benzophenonetetracarboxylic dianhydride or diimide, cyclopentanetetracarboxylicdianhydride or diimide, cyclohexanetetracarboxylic dianhydride ordiimide, pyromellitic dianhydride or diimide, etc.

PROCEDURE As mentioned above, a feature of the present invention is thatcross-linking of the prefonned polymer takes place under phaseboundary-limited reaction conditions. This means that component A andcomponent B must be present on the fibrous substrate in separate phasesso that the cross-linking reaction will take place at the boundarybetween the phases. This is, of course, a very desirable situation asunder such conditions the cross-linking takes place almostinstantaneously so that no aftertreatment (curing) is required. Theboundary may be between different types of phases-solid, liquid, orgaseouswith the proviso that at least one phase must be fluid, i.e.,liquid or gaseous. Thus, the component A may be present as a solid phase(e.g., applied in solution, followed by evaporation of solvent) andcomponent B as a liquid or gas phase. Where component A is applied as aliquid phase, component B is applied as a solid, liquid, or gas phase,Generally, a system of liquid-liquid phases is preferred, andparticularly wherein the phases are mutually insoluble whereby topreserve the boundary between the phases. Thus in a preferred embodimentof the invention, the selected components A and B are formed intoseparate solutions, using solvents which are substantially mutuallyimmiscible. Thus, for example, component B is dissolved in water andcomponent A is dissolved in benzene, carbon tetrachloride, toluene,xylene, ethylene dichloride, chloroform, hexane, octane, petroleum etheror other petroleum distillate, or any other inert, water-immisciblesolvent. The two solutions are then applied to the fibrous substrateserially; that is, the substrate is treated first with one solution,then with the other. The order of applying the solutions is notcritical. Generally, the solution of component B is applied first andthe solution of component A is applied next. However, the reverse ordergives good results and it is within the ambit of the invention to applythe solutions in either sequence.

The solutions may be applied to the fibrous material in any way as longas they are applied serially. A preferred method involves immersing thematerial in one solution, removing excess liquid as by the use ofsqueeze rolls, immersing the material in the second solution, and againremoving excess liquid. To remove unreacted materials, solvents, etc.,the material may then be washed and/or rinsed. Then, after drying, it isready for use or sale. Conventional apparatus consisting of tanks,padding rolls, squeeze rolls, and the like are generally used inapplying the respective solutions. The amount of each component appliedto the fibrous material may be varied by altering the residence time inthe solutions, the pressure exerted by the squeeze rolls, and by varyingthe concentration of the active ingredients in the respective solutions.To decrease carryover of the solvent from the first treating solution tothe second solution, the fibrous substrate after its immersion in thefirst solution may be subjected to drying conditions such as exposure toa current of warm air to evaporate at least part of the solvent andhence concentrate the solution carried by the fibers.

As noted above, a critical factor in the preferred form of the inventionis that the complementary agentscomponent A and component Bare seriallyapplied to the textile dispersed in solvents which are substantiallymutually immiscible. The nature of the solvents is of no consequence aslong as they are essentially inert and possess the above-stated propertyof substantial immiscibility. Usually, volatile solvents are preferredas they may be removed from the treated textile by evaporation. However,nonvolatile solvents can be used, in which case they may be removed fromthe product by extraction with suitable volatile solvents therefor orwashed out with soap and water or detergent and water formulations. lnsome cases component A is soluble in water and may thus be applied tothe textile in aqueous solution. In such case the solvent for componentB may be any inert, essentially water-immiscible organic solvent.Typical illustrative examples thereof are benzene, toluene, xylene,carbon tetrachloride, ethylene dichloride, chloroform, hexane, octane,petroleum ether or other volatile petroleum fraction. Usually, however,component A, because of its high molecular weight, is insoluble in waterand is preferably applied in solution in a substantiallywater-immiscible organic solvent, such as any of those listed above. Insuch case, component B would be applied in aqueous solution. It is, ofcourse, obvious that many of the contemplated highly reactive groupswill react with water (e.g., isocyanate, carbonyl halide, sulphonylhalide, carbamyl halide, haloformate, anhydride, and imide groups) andhence components which contain these are not normally applied in aqueoussolutions.

Although one of the complementary solutions generally has water as asolvent, such a system is not essential and one may utilize a system oftwo essentially immiscible organic solvents, component A being dispersedin one solvent and component B in the other. As an example, component Amay be dispersed in 2-bromoethyl acetate and component B dispersed inbenzene. Another example involves using formamide, dimethylformamide, ordiethylformamide as the solvent for component A and using n-hexyl etheras the solvent for component B. A further example involves a system ofadiponitrile as the solvent for component A and ethyl ether as thesolvent for component B. Examples of other pairs of solvents which aresubstantially immiscible with one another and which may be used forpreparing the solutions of the respective reactants are 2- bromoethylacetate and n-hexyl ether, ethylene glycol diacetate and n-hexyl ether,adiponitrile and n-butyl ether, adiponitrile and carbon tetrachloride,benzonitrile and formamide, n-butyl ether and formamide, di-N-propylaniline and formamide, isoamyl sulphide and formamide, benzene andformamide, butyl acetate and formamide, benzene and nitromethane,n-butyl ether and nitromethane, carbon tetrachloride and formamide,dimethyl aniline and formamide, ethyl benzoate and formamide.

The concentration of active materials (component A and component B) inthe respective solutions is not critical and may be varied widely.Generally, it is preferred that each of the pair of solutions containsabout from 0.5 to 20 percent of the respective active component. inapplying the process of the invention, enough of the respectivesolutions are applied to the fibrous substrate to provide a cross-linkedpolymer on the fibers in the amount desired. In treating some substratessuch as textiles it is desired to limit the amount of cross-linkedpolymer to about 1 to percent of the weight of the textile,

whereby to achieve the desired modification-cg, shrinkproofing-withoutdamaging the hand of the textile.

It is often desirable to add reaction promoters or catalysts to eitherof the solutions of components A or B in order to enhance reactionbetween the active agents. For example, in cases where the systeminvolves reaction between (1) amine or hydroxy groups and (2) carbonylchloride, sulphonyl chloride, carbamyl chloride, or chloroformategroups, it is desirable to add to the solution of the componentcontaining the amine or. hydroxy groups a sufficient amount of alkalinematerial to take up the HCl formed in the reaction. For such purpose onemay use a tertiary amine such as pyridine, dimethyl aniline, orquinoline or an alkali-metal hydroxide, or, more preferably, an alkalinematerial with buffering capacity such as sodium carbonate, sodiumbicarbonate, trisodium phosphate, borax, sodium metasilicate, etc.Another plan which may be used in instances where one component containsamino groups, involves supplying said component in excess so that itwill act both as a reagent and as an HCl-acceptor. The reaction ofcomponents A and B may also be catalyzed by addition of such agents astributyl tin chloride, stannous tartrate, ferric chloride, titaniumtetrachloride, boron trifluoride-diethyl ether complex, or tin salts offat acids such as tin laurate, myristrate, etc. Such catalysts areparticularly useful to promote reaction between components containinghydroxy groups and those containing isocyanate, acid chloride, orchloroformate groups.

Where one of the solutions of the reactants contains water as thesolvent, it is often desirable to incorporate a minor proportion of asurface-active agent to aid in dispersing the reactant and to assist inpenetration of the solution into the textile. For this purpose one mayuse such agents as sodium alkyl (Cg-C1 sulphates, the sodium alkane (C-C sulphonates, the sodium alkyl (CgC2o) benzene sulphonates, esters ofsulphosuccinic acid such as sodium dioctylsulphosuccinate, and soaps,typically sodium salts of fat acids. Emulsifying agents of the nonionictype are suitable, for example, the reaction products of ethylene oxidewith fatty acids, with polyhydric alcohols, with partial esters of fattyacids and polyhydric alcohols or with alkyl phenols, etc. Typical ofsuch agents are a polyoxyethylene stearate containing about 20oxyethylene groups per mole, a polyoxyethylene ether or sorbitanmonolaurate containing about 16 oxyethylene groups per mole, adistearate of polyoxyethylene ether of sorbitol containing about 40oxyethylene groups per mole, iso-octyl phenyl ether of polyethyleneglycol, etc. Generally, only a small proportion of surface-active agentis used, on' the order of 0.05 to 0.5 percent, based on the weight ofthe solution. In addition to, or in place of the surface-active agent, asupplementary solvent may be added to the primary solvent (water) inquantity sufficient to disperse the active reactant. For such purposeone may employ acetone, or other inert, volatile solvent, particularlyone that is at least partially miscible with water. It is evident thatthe solutions of components A and B need not necessarily be truesolutions; they may be colloidal solutions, emulsions, or suspensions,all these being considered as solutions for the purposes of the presentinvention.

Ordinarily, the treatment of the fibrous substrate with the solutions ofthe complementary agents is carried out at room temperature as at suchtemperature the polymerization takes place very rapidly, that is, in amatter of a minute or less. If, however, a higher rate of polymerizationis desiredas in continuous operation on long lengths of cloththe secondsolution may be kept hot, for example, at a temperature of 50 to C.Also, where the agents used include a polyol as such (in contrast to thealkali salt thereof) it is preferable to heat the second solution as thecross-linking rates with the polyols are generally unsatisfactory atroom temperature.

As has been explained above, in the preferred modification of theinvention the solutions of components A and B are serially applied tothe fibrous material in the form of mutually immiscible solutions toprovide a liquid-liquid interface between the solutions as they areserially laid onto the fibers. In a lesspreferred modification of theinvention, a system is used which utilizes a solid-liquid interface.Such a system is established in the following way: The fibrous materialis first impregnated with a solution of one of the complementaryagents-for example, component A-dispersed in an inert, volatile solvent.The substrate is then subjected to drying as by exposing it to a currentof hot air. The fibers which are now covered with a deposit of the firstcomponent in a solid state, are then impregnated with the complementaryagentcomponent B, in this case, dispersed in an inert, preferablyvolatile solvent. In this way the fibers are layered with a superposedsystem of solid component A and a solution of component B. Under theseconditions cross-linking takes place rapidly, forming thethree-dimensional polymer in situ on the fibers. In this system it isnot essential that the respective solvents be immiscible. Thus, forexample, component A may be applied in water solution and component B ina water-miscible solvent such as dioxane or acetone. This and otherphases not involv ing liquid-liquid boundary cross-linking are describedin some ofthe examples below, e.g., example l, runs 2 and 4.

In a preferred embodiment, the invention is applied to wool as thefibrous substrate whereby to attain such desirable results as increasingthe resistance of the textile to shrinking and felting when subjected towashing operations, increasing the resistance of the textile to becomingsoiled in use, enhancing resistance to bleaches and to light, decreasingthe tendency of the textile to becoming creased or wrinkled during wearor during washing and drying operations, i.e., to provide it witheasy-care" properties so that ironing after laundering is largelyeliminated. Moreover, these desirable effects are attained withoutimpairing such desirable properties as tensile strength, abrasionresistance, elasticity, porosity, and hand of the material so thattextiles modified in accordance with the invention may be used infabricating garments of all kinds. The invention may be applied to woolin any physical form. for example, bulk fibers, top, sliver, roving,webbing, yarn, felt, woven textiles, knitted textiles, completedgarments or garment parts, and other fabricated forms such as carpets,rugs,

blankets, cords, tapes, etc. As noted hereinabove, the permanence ofmodification obtained in accordance with the invention is primarilybased on converting the preformed polymer into an insoluble,cross-linked (three-dimensional) 3- dimensional) structure. However, itis evident that in treating wool in accordance with the invention, onemay additionally obtain a chemical combination of the polymer with thewool in such cases where the preformed polymer and/or the fixativecontains groups capable of reacting with reactive sites on the woolmolecules. Since such reactive sites are primarily of an amine orhydroxy nature, it is believed that chemical combination (grafting)occurs in such instances where the agents applied (components A or B)contain such reactive groups as carbonyl halide, haloformate, sulphonylhalide, carbamyl halide, isocyanate, etc.

Although the invention is of particular advantage in its application towool, this is by no means the only type of fiber which comes into theambit of the invention. Generically, the invention is applicable to thetreatment of any type of fibrous material, for example, animal hides andleather; silk, animal hair, mohair; cotton; sisal; hemp; jute; ramie;flax; wood; paper; synthetic cellulosic fibers such as viscose,cellulose acetate, cellulose acetate-butyrate, saponified celluloseacetate, cupraammonium rayons, ethyl cellulose; polyvinylalcohol-protein fibers; algin and pectin fibers; glass fibers; asbestos;organic noncellulosic fibers such as polyethylene terephthalate,polyacrylonitrile, polyethylene, polypropylene, polyvinyl chloride,polyvinylidene chloride, nylon, polyurethanes; regenerated proteinfibers such as those prepared from casein, soybeans, peanut protein,zein, gluten, egg albumin, collagen, or keratins such as animal hoof orhorn; mixtures of any of the above such as textiles containingcellulosic and noncellulosic fibers, blends of synthetic fibers orcotton with wool, etc. The invention may be applied to such fibrousmaterials in any state such as bulk fibers, staple fibers, slivers,yarns, woven or knitted textiles, felts, fabricated articles such asgarments and garment parts. The application of the invention may be forthe purpose of obtaining any of a wide variety of functional ordecorative effects such as sizing, increasing gloss or transparency,increasing water-, oil-, or soil-repellency, increasing adhesion orbonding characteristics of the substrates with rubber or otherelastomers, imparting softness or lubricity, imparting shrinkageresistance, decreasing tendency to wrinkle, crease and pill during wearor during washing and drying operations, etc. In cases where the fibrousmaterial is a hydrogen donor (that is, where its molecules containactive hydrogen as in amine or hydroxy groups), it would be expectedthat during application of the process of the invention, a chemicalcombination of the polymer to the fiber molecules will take place,particularly where either the preformed polymer or the fixative containssuch highly reactive groups as carbonyl halide, sulphonyl halide,carbamyl halide, haloformate, or isocyanate. Typical examples ofhydrogen donor fibers (in addition to wool) are the natural cellulosicfibers, viscose rayons, saponified cellulose acetate fibers, etc.

Having now described the types of compounds which may be used ascomponents A and B and how they are applied to fibrous materials, wewill next explain the various preferred embodiments of the invention. Inthe procedure of the invention, the type of preformed polymer employedis the determinative factor because of the large molecular weightthereof in comparison to that of the fixative or the cross-linking unitsderived therefrom. Accordingly, the various subgeneric embodiments ofthe invention are based on the type of preformed polymer, i.e.,component A.

EMBODIMENT l In this preferred embodiment of the invention, component Ais an addition polymer. Numerous examples thereof are listed hercinabovein the sections entitled Component A (Addition Polymers)" and ComponentA (Converted Addition Polymers) Among the special advantages of additionpolymers for use as component A are stability to oxidation and light,good film-forming ability, availability of a wide spectrum of types andindividual species, and the fact that many are relatively inexpensivecompared to other classes of polymers.

In the preferred practice in accordance with this embodiment of theinvention, component A is an addition polymer containing (as the highlyreactive groups) carbonyl halide, sulphonyl halide, haloformate,isocyanate, carbamyl halide, or anhydride groups and is applied to thefibrous substrate in the form of a solution in an inert, essentiallywater-immiscible solvent. The complementary fixative (component B) isaccordingly applied as an aqueous solution and contains hydroxy groups,or, more preferably, amine or imine groups as the highly reactive groupscomplementary to those on component A. Thus in operating in the sphereof the preferred modification of this embodiment, component B may bechosen from any of the types exemplified above in the section entitledComponent B (Fixative) Containing Nl-I or NH Groups."

Coming under special consideration is the use, as component A, ofcopolymers of (a) methacryloyl chloride or acryloyl chloride (to providefree COCl groups) with (b) other polymerizable unsaturated monomers freefrom highly reactive groups, typically such monomers as olefines, estersof acrylic or methacrylic acid, vinyl esters and ethers, vinyl chloride,etc.

Especially useful are the copolymers containing units derived from (1)acryloyl or methacryloyl chloride and (2) from an olefine such asethylene, propylene, isobutylene, or butadiene. Usually, a third type ofunit is included to decrease crystallinity and to increase solubility.For these purposes, the copolymer may contain units derived from (3)esters of acrylic or methacyrlic acid, vinyl esters of fatty acids,vinyl ethers, vinyl chloride, or the like. These copolymers may bedirectly prepared from the monomers. More usually, acrylic ormethacrylic acid is copolymerized with the olefine and the third type ofmonomer and the product is treated to convert the free acid groups tocarbonyl chloride groups. Thus although not made directly, the finalproduct can still be considered as a copolymer of acryloyl ormethacryloyl chloride with the olefine and the third type of monomer. Atypical formulation for this type of copolymer would be, for example, 1to 10 mole percent of methacryloyl chloride, 5 to 10 mole percent ofvinyl acetate, or the like, and the remainder (to mole percent) of theolefine.

This embodiment l of the invention is further demonstrated by thefollowing illustrative examples:

EXAMPLES Accelerotor Shrinkage Test: This test for shrinkage wasconducted in the following way: The wool samples were milled at 1,700rpm. for 2 minutes at 40-42 C. in an accelerotor with 0.5 percent sodiumoleate solution, using a liquor-towool ratio of 50 to 1. After thiswashing operation the samples were measured to determine their area andthe shrinkage was calculated from the original area. The accelerotor isdescribed in the American Dyestuff Reporter, Vol. 45, p. 685, Sept. 10,I956. The two-minute wash in this device is equal to about 15 homelaunderings.

Washing Machine Shrinkage Test: The wool samples were washed in areversing agitator-type household washing machine, using a 3-lb. load, awater temperature of F., and a lowsudsing detergent in a concentrationof 0.1 percent in the wash liquor. The wash cycle itself was for 75minutes, followed by the usual rinses and spin drying. In most casesthis washing program was repeated several times. The damp material wasthen tumble-dried in a household-type clothes dryer. The samples werethen measured to determine their length and width and the shrinkagecalculated from the original dimensions.

Oil Repellency Test: The 3M oil repellency test described by Grajeck andPetersen, Textile Research Journal, 32, pp. 320-33l, 1962. Ratings arefrom 0 to 150, with the higher values signifying the greater resistanceto oil penetration.

Ratings are from to 100 with the higher values signifying greaterresistance to water penetration.

EXAMPLE 1 1. Solution A: Component A was a terpolymer of ethylene (80percent), vinyl acetate percent), and methacryloyl chloride (5 percent).Its molecular weight was about 50,000 and it contained about 40-50carbonyl chloride groups per polymer molecule. Solutions were made ofthis terpolymer in methyl chloroform at concentrations of 3 percent and1.5 percent.

2. Solution B: 0.5 percent hexamethylene diamine (component B), 1percent sodium carbonate, and 0.05 percent wetting agent (isooctylphenylether of polyethylene glycol) in water.

3. A sample of wool cloth was immersed in one solution at roomtemperature for about 30 seconds, run through squeeze rolls to removeexcess liquid, immersed for about 30 seconds in the complementarysolution at room temperature, run through squeeze rolls to remove excessliquid, rinsed in water, and dried in air at room temperature.

4. The sequence of treatment with the respective solutions and theresults of shrinkage tests on the products are tabulated below:

Order Cone. of Area shrinkage Run solutions terpolymer (Accelerotor),

in Sol. A, k

l BA 3 8.8 2 B'A 3 4.9 3 B-A L5 6.9 4 B'-A 1.5 4.9 5 A-B 3 3.0 Control29,0

(Untreated wool) ln these cases, the cloth, after application ofsolution B, was air dried prior to immersion in solution A.

EXAMPLE 11 Percent area shrinkage, cumulatlve' te Cone. of r- Order ofterpolymnr applying in Sol. Wash Wash Wash Wash Run solutions percent 12 4 1 A-B 3 0. 2 0. 5 0.3 0. 5 2 1 0. 2 0. 9 0. 4 0. 1 3.. 0.5 1.0 3.54.7 9.4 4 8 0. 3 1. 5 0. 5 0. 5 Control 19. 30. 5 35. 5 39. 5

Successive 75-minute washes in automatic home washing machine, agitatortype. See text above for details of wash method.

The products of runs 1, 2, and 3 were subjected to tests for abrasionresistance, using a Stoll flex abrader, ASTMzDl 175-551. The results areas follows:

Wt. resin Abrasive resistance. Run on fabric, cycles to break 1: WarpFill l 3 810 767 2 l 716 969 3 0.5 550 588 Control 0 657 547 (Untreated)The products of runs 1, 2, and 3 were tested for their coefficient offriction by drawing individual fibers over a glass rod in the directionagainst the scales. In this test a smaller value indicates a smootherfiber surface. The results are given below:

Wt. resin I Friction coefficient Run on fabric. (against scales) Control0 0.130 (Untreated EXAMPLE Ill Diamine Abbreviation Ethylene diamine EDAI,3-Diarninopropanc DPA Propylene diamine PDA Hexamethylenc diamine HMDAPiperazine Pip Wool cloth was treated with the solutions as in example1, part 3. in all cases the sequence of treatment was B-A. The resultsare given below:

Percent area shrinkage, cumulative alter- Component B used Wash 1 Wash 2Wash 3 Wash 4 EDA 0.9 1.1 2.0 1.2

DPA 0. 8 2. 5 3. 4 3. 1

PDA 1.5 1.0 2.8 2.5

HMDA 1.0 0.1 0 0. 5

Pip 2. 8 9. 1 15. 5 21.21

Control l9. 1 30, 5 35. 4 39. 5

Successive 75-minute washes in automatic home washing machine, as(inscribed above.

EXAMPLE lV Solution A: The same terpolymer as in example 1 was dissolvedin methyl chloroform (or Stoddard solvent) at a concentration of 1.5percent.

Solution B: Same as in example [11.

Wool cloth was treated with the solutions as in example 1, part 3. Inall cases, the sequence of treatment was B-A. The results are givenbelow:

Percent area shrinkage, cumu- Comlative ter Solvent for component Runponent A B used Washl Wash 2 Wash 3 Wash 4 1 Miethyl ehloro- EDA 1.3 2.03.0 1.3 0. 7 2. 5 3. 2 3. 5 DA 1. 0 1. 0 2. 5 2. 2 HMDA 0.2 0.5 0.2 0 1.2 1. 5 2. 7 2. 2 0 0 0 0. 7 0----. 1 DA 0.8 0.6 0.3 0.7 Control 18. 830. 5 36. 4 39. 5

Successive 75-minute washes in automatic home washing machino, asdescribed above.

2.5. EXAMPLE V A solution of 95 ml. styrene, ml. methacryloyl chloride,and 1,000 ml. of benzene, containing 0.2 g. azo-bis-isobutyronitrile,was swept with dry nitrogen for 30 minutes and then heated to 7080 in aclosed vessel for 8 hours. The resulting solution of thestyrene-methacryloyl chloride copolymer (containing more than 3 carbonylchloride groups per molecule) was used to treat test swatches of wool asin example l, part 3. Various aqueous solutions of diamines were used inthe first treatment step; these diamine solutions contained 0.5 percentof the specified diamine, 1.0 percent sodium carbonate, and 0.1 percentwetting agent. Abbreviations for diamines are given in example II].

A copolymer of methyl methacrylate and methacryloyl chloride (containingover three carbonyl chloride groups per copolymer molecule) was preparedas follows: 95 ml. of methyl methacrylate (redistd) and 5 ml. ofmethacryloyl chloride were placed in 500 ml. of dry benzene. The systemwas flushed with dry nitrogen, 0.1 g. azo-bis-isobutyronitrile added,and heated at 7080 C. for 6 hours while held in a closed vessel.

The resulting copolymer solution was used to treat test swatches of wool(14 inch by 14 inch): The test piece was first immersed in a solution,at room temperature, of 0.5 percent ethylene diamine in H O (containing1.0 percent sodium carbonate and 0.1 percent wetting agent), then passedthrough squeeze rolls to give a wet pickup of about 60 percent. Theswatch was then immersed in the copolymer solution, at room temperature,and again passed through the squeeze rolls, followed by a light15-minute wash in 0.1 percent detergent solution, and finally dried atroom temperature. The treated material shrank only 12 percent in a75-minute wash in home washing machine, compared to 22 percent shrinkageby an untreated swatch.

EXAMPLE VIl A copolymer of lauryl methacrylate and methacryloyl chloride(in 95/5 mole ratio) was prepared by a standard bulk polymerizationtechniquei.e., heating in a closed vessel at 80 for 5 hours in thepresence of a minor proportion of 01,11- azodiisobutyronitrile as apolymerization initiator. The copolymer contained three or more carbonylchloride groups per molecule.

Solution A: The copolymer above was dissolved in toluene at aconcentration of 5 percent and 2.5 percent.

Solution B: 4 percent ethylene diamine, 7 percent sodium carbonate, and0.01 percent wetting agent (isooctylphenyl ether of polyethylene glycol)in water.

Wool cloth was treated with the above solutions as in example 1, part 3,applying the solutions in the order B-A. in a control run, impregnationin solution B was omitted.

The products were tested for shrinkage and also for permanence of thecopolymer deposit by extraction with benzene for 2% hours in a Soxhletextractor. The results are tabulated below:

Successive 75-minute washes in automatic home washing machine, asdescribed above.

1 Shrinkage tested after extraction.

3 Not determined.

3 Shrinkage tested before extraction.

EXAMPLE Vlll Treatment of wool with a terpolymer containing styrene,

lauryl methacrylate and methacryloyl chloride, the terpolymer containingthree or more carbonyl chloride groups per molecule.

The terpolymer was prepared, using the following recipe:

52 ml. styrene 30 ml. lauryl methacrylate 10 ml. methacryloyl chloride900 ml. benzene 0.2 g. azo-bis-isobutyronitrile The system was sweptfree of air by sweeping with dry nitrogen and was kept under a nitrogenatmosphere during 10 hours of heating in a closed vessel at 80 C. Theresulting terpolymer solution was used to treat wool swatches: The testswatches were first dipped in a 0.5 percent aqueous solution of adiamine, passed through a squeeze roll, then immersed in the terpolymersolution, again passed through the squeeze roll, and finally given alight wash in 0.1 percent detergent solution and dried at roomtemperature. The following results were obtained when the swatches werewashed in an accelerated shrinkage test, using the accelerotor:

Step 1 Step 2 Area shrinkage, 3i:

HMDA Terpolymer soln. 12.6 EDA Terpolymer soln. 5.0 Control 30.0(Untreated) EXAMPLE IX 1,1-Dihydroperfluorooctyl acrylate (9 moles),methacryloyl chloride (1 mole), and 11,0:-azodiisobutyronitrile (about 5g.) as a polymerization initiator were heated together at 78 C. for 3 to4 hours in a closed vessel. The resulting copolymer containing three ormore pendant COCl groups per molecule was a tacky, solid resin.

Solution A: The above polymer was dissolved in 1,3- bis(trifluoromethyl) benzene at a concentration of 3 percent.

Solution B: 2 percent hexamethylene diamine, 2 percent sodium carbonate,and 0.01 percent wetting agent (isooctylphenyl ether of polyethyleneglycol) in water.

Wool cloth was treated with these solutions as in example 1, part 3,applying the solutions in the order BA. In a control run, impregnationin solution B was omitted. increase in weight in both cases was 1percent. The products were tested for oil and water repellency asprepared and after extraction with benzotrifluoride for 6 hours in aSoxhlet extractor. The results are given below:

EXAMPLE X The chloroformate of ethylene glycol methacrylate The productwas extracted with acetone for 6 hours and it was found that the productretained 93 percent of the resin deposit.

CH:C"C GH CH OCC1. Solution A: component A was chlorosulphonatedpolyethylene of number average molecular weight about was prepared in 95percent overall yield by reaction of 30,000 and of the formula ethyleneglycol monomethacrylate with excess phosgene. The

chloroformate was purified by distillation, b.p. 85 C. at 3 mm.

The chloroformate was copolymerized with lauryl 0H QH -CH CH-CHzCHzCHz-CII methacrylate to produce a copolymer containing at least three 50m nchloroformate groups per molecule, using the following technique: 1 5

Lauryl methacrylate g.), 5 g. of the chloroformate, 100 wherein n isapproximately 17 and x is approximately l2. lt ml. dry benzene, and 200mg. a,a'-azodiisobutyronitrile were was dissolved in benzene at aconcentration of 1.5 percent. heated ina closed vessel at 79 C. for 18hours. Solution B: 0.5 percent of hexamethylene diamine (HM- Solution A:The copolymer solution prepared as given D of hyl diamifle 1 PercentSodium above. 20 bonate, 0.05 percent of wetting agent (isooctylphenylether of Solution B: Three percent hexamethylene diamine and 0.01polyethyleneglycol) in water.

P rcent Wetting agent (isooctylphenyl ether of polyethylene Wool clothwas treated with these solutions as in example I,

glycol) in water. part 3, applying the solutions in the order 8 (roomtempera- Wool cloth was treated with the above solutions as in examture,immersion time I min.)A (60 C., immersion time 2 ple l, part 3, applyingthe solutions in the order B-A. In a conmin.). The results are givenbelow: trol run, impregnation with solution B was omitted.

The products were tested for shrinkage before and after an Component B71 Area shrinkage, cumulative extraction with chloroform20 hours in aSoxhlet extractor. used wash 1 2 3 4 The results are given below:

1 HMDA 0.3 1.9 3.7 5.0 2 EDA 0.5 3.9 6.7 11.5 Control 19.1 30.5 35.439.5

Approx. Percent area shrinkf of accelerator Successive 75-minute washesin automatic home washing machine. as described resin 011 "'"T' abovefabric, Before After Procedure percent extraction extraction Inaccordance with invention 15 2 5 Control (N 0 treatment with Sol. B)- 150 12. 6

Blank (No treatment) 30 7M, i i i i N EXAMPLE Xlll 40 Wool cloth wasimmersed in a solution containing l0 per- EXAMPLE XI cent ethylenediamine in acetone. The cloth was squeezed to remove excess liquid andair-dried to remove the solvent. It

Solution A: Component A was a l/ l copolymer of methyl was then immersedin a 5 percent solution of the vinyl ether and maleic anhydride having aspecific viscosity of chlorosulphonated polyethylene (as in example Xll)for 2 1.0 to 1.4 (as 1 percent solution in methyl-ethyl ketone at 25minutes, squeezed and air-dried.

C.). The repeating unit of this copolymer had the structure A piece ofthe treated cloth and a control (untreated) piece were placed in 5percent sodium hypochlorite solution in water and observed to ascertaindissolution time of each.

2 The results are given below: CHzOH-CHCH- O:C\ 6 0 lilapsedntlir'tlicUrltgjgifglfloth Treated cloth l0 Vigorous evolution No evidence It wasdissolved in ethyl acetate at concentrations of 3, L5, 20 zi iygg s mackand 0.7 percent. 120 Completely dissolved Still essentially Solution B:2 percent hexamethylene diamine, 3 percent wh l a a sodium carbonate,and 0.01 percent wetting agent (isoocedges tylphenyl ether ofpolyethylene glycol) in water.

Wool cloth was treated with the above solutions as in example I, part 3,using the sequence B-A. EXAMPLE XIV Tests for permanency of the finishwere conducted by measuring loss in weight after extraction for 6 hourswith acetone. A copolymer of methacryloxymethyl pentamethyldisiloxaneThe product retained 95 percent of the resin deposit in this test. In acontrol test wherein treatment with solution B (the CH CH O fixative)was omitted, the cloth retained only 24 percent of the l H In otherruns, wool cloth was immersed in an acetone solu- CH3 CH3 CH3 tion ofthe copolymer, squeezed to remove excess liquid, air i dried toevaporate the acetone, immersed in an aqueous solution of 4 percenthexamethylene diamine, 7 percent sodium and the chloroforrnate ofmonoethylene glycol methacrylate carbonate, and 0.01 percent wettingagent (isooctylphenyl CH O ether of polyethylene glycol), then rinsed inwater and air- 1 3 H dried. 7 CH :C-COCH;QHOCOC1 was prepared by heatingthe following ingredients in a closed vessel at 75 C. for hours:

1 .5 grams of the siloxane compound as above 0.8 gram of thechloroformate compound as above cc. dry toluene (diluent) 0.1 gramma-azobisisobutyronitrile (polymerization initiator) The viscous syrupresulting was diluted with additional toluene to 3 percent and 6 percentconcentrations and used as solution A.

Solution B was a 5 percent solution of hexamethylene diamine and about0.01 percent nonionic wetting agent in water.

Wool cloth was treated with the solutions as in example I, part 3, usingthe sequence B-A. The results of tests on the products are given below:

Extraction was with benzene. 3 hours in a Soxhlet extractor.

EMBODIMENT 2 In accordance with this embodiment of the invention,component A is a polyalkylene imine. Typical examples of such polymersare exemplified above in the section entitled Component A (Polyalkylenelmines). A special feature of these polymers is that they containbuilt-in highly reactive groups on the polymer backbone, namely, NHgroups. In addition, they contain terminal NH groups. Another feature isthat they are soluble in water even at very high molecular weights,e.g., 10,000 and above. Accordingly, they may advantageously be appliedto the fibrous material in the form of an aqueous solution. The fixative(component B) in such case is then preferably applied as a solution inan inert, substantially water-immiscible solvent. Component B ispreferably chosen to provide isocyanate radicals as the complementary,highly reactive groups. Other fixatives which provide excellent resultsare those containing carbonyl halide, haloformate, or anhydride groups.Thus the preferred types of compounds for use as the fixative may beselected from those exemplified above in the sections pertaining tocomponent B of the types containing NCO, COX, OCOX, or anhydride groups.

This embodiment 2 of the invention is further demonstrated by thefollowing illustrative examples:

EXAMPLE XV Component A was a polyethylene imine of molecular weightabout 30,00040,000. Basically, this polymer had the structure Cone. ofPercent area shrinkage, Compocumulative a1ter nent A Wt. resin Order ofin S0]. A, Compoon fabric, Wash Wash Wash treatment percent nent Bpercent 1 3 5 3 T DI 2. 3 0 0 0 4 TDL. 3.6 0 1.0 2. 0 1 TDI". 1.0 0 1. 01.0 0.5 TDI 0.45 0 1.0 2.0 0.25 'Il)l 0.22 0 1.0 1.5 3 SC 2.!) l) 1.02.0 3 SC 2. 8 0 l. 0 2. 0 2 SC 1.4 0 1.0 3.0 10 None 0. 6 3. 0 13. 5 20.0

None .do... None 0. 0 26. 0 38.4

Successive 75-minute washes in automatic homo washing machine, agitatortype, as described above.

Several of the products as prepared above were subjected to extractionwith acetone for 3 hours in a Soxhlet extractor to test the permanenceof the cross-linked resin deposits. Also, shrinkage tests weredetermined after such extraction. The results are tabulated below:

Conc. of Wt. of resin on Compofabric, percent Area shrinkage nent A in(Accelerator, Order of Sol.A, Compo- Before After exafterextractreatment percent nent B extraction traction Lion), percent 3 TDI2. 3 1. 7 0 4 TDL... 3.6 3.2 2.0 3 SC 2. 9 2. 3 2. 0 3 SC 2.8 2.2 2.0

10 None 9. 6 2. 6 10.0 None d0 27.0

EXAMPLE XVl Solution A: Aqueous solution of the polyethylene iminedescribed in example XV (concentration given below) plus ca. 0.01percent nonionic wetting agent.

Solution B: Acetone solution containing 4 percent pyromel liticdianhydride.

Wool swatches were treated in the following manner: The swatches werewet-out in solution B, passed through a squeeze roll to obtain about apercent wet pickup, and air-dried at room temperature for about 20minutes to remove the acetone solvent. The dried swatches were thenimmersed in solution A at room temperature for one minute, passedthrough a squeeze roll to 90 percent wet pickup, washed to removeunreacted materials, and air-dried.

The various products were tested for permanence of the resin deposit byextraction with acetone for 3 hours in a Soxhlet extractor. Shrinkagewas also tested after extraction. The results are given below:

Wt. of resin on fabric,

percent Area shrinkage (Accelerotor, after Conc. 01 Component A BeforeAfter extraction),

in S01. A extraction extraction percent EXAMPLE XVll Wool swatches wereimmersed in an aqueous solution containing 3.3 percent of polyethyleneimine (as described in example XV) and passed through squeeze rolls to apercent wet pickup. The swatches were air-dried at room temperature. Thecloth was placed in a cylinder wherein it was exposed to a current ofnitrogen carrying vapors of toluene diisocyanate. Following thistreatment, the wool was washed and air-dried.

This product and a control, in which the exposure to toluenediisocyanate. was omitted, were tested by extraction with acetone for 3hours in a Soxhlet extractor. Shrinkage tests were also conducted beforeand after extraction. The results are tabulated below:

w of resin Area shrinkage on f b i (Accelerotor). Before 7 After BeforeAfter Procedure extraction extraction extraction extraction inaccordance with invention 3.4 L7 4.0 6.9 Control 3.3 18.0 26.0

(No application of TDI) Blank 27.0

EMBODIMENT 3 In accordance with this embodiment of the invention,component A is a polyurethane, or, more accurately, a polyether (orpolyester) containing internal urethane groups and free isocyanategroups. Typical examples of such polymers are exemplified above in thesections entitled Component A (PolyethersY and Component A(Polyesters)", wherein it is explained that these polymers may beprepared by reacting a polyether (or polyester) containing hydroxygroups with an excess of a diisocyanate. An advantageous feature of thepolyurethanes is that when they are cross-linked in the phaseboundary-limited reaction, they are converted into urethane elastomersand as a result the treated textile material exhibits an especially softand full hand.

Ordinarily, the polyurethane will contain free isocyanate radicals asthe highly reactive groups and since these are water-sensitive, thepolymer is applied to the fibrous substrate in the form of an inert,essentially water-immiscible solvent such as benzene, toluene, or thelike. The fixative (component B) is then preferably applied as anaqueous solution. Component B is preferably chosen to provide amine orimine radicals as the complementary, highly reactive group. Typicalexamples are given above in the section entitled Component B (Fixative)Containing Nl-l or NH groups.

In a variation of the basic procedure of this embodiment, one mayapplyas component Aa polymer of the class of polyethers (or polyesters)containing free hydroxy groups. Typical examples of these are given inthe above sections entitled Component A (Polyethers) and Component A(Polyesters)". In such case one would utilize as component B a compoundcontaining free isocyanate groups (such as those exemplified above inthe section entitled Component B (Fixative) Containing NCO Groups"). Insuch case the end result of the phase boundary-limited reaction will bea cross-linked polyurethane polymer.

This embodiment 3 of the invention is further illustrated below:

EXAMPLE XVlll APPLICATION OF AN lSOCYANATE-CONTAINING POLYURETHANE TOWOOL Poly(propylene oxide) glycol of an average molecular weight 2000and a hydroxyl number of 56 was chain-extended and end-capped with2,4-tolylenediisocyanate in the following manner: A dry, 3-neck, SOD-ml.flask, fitted with stirrer, dropping funnel, nitrogen inlet andthermometer was charged with 100 g. (0.05 mole) poly(propylene oxide)glycol (average molecular weight 2000) and this was heated with stirringunder nitrogen to 75 C. Tolylene diisocyanate (17.4 g.0.l mole) was thenadded slowly over a -20 minute period via the dropping funnel. Themixture was stirred at 75-80 C. for 3 hours. An infrared spectra of theviscous syrup showed no free OH but did show the expected strong band at4.4 microns (N=C=O) and a weak band at 5.8 microns arising from chaincoupling). The polymer was dissolved in dry toluene. Polymerconcentrations of 9 and 2 percent were used as solution A. The aqueoustreating solution B contained 4 percent (by volume) oftriethylenetetramine and ca. 0.01 percent of the wetting agent(isooctylphenyl ether of polyethylene glycol).

Wool cloth was treated with the solutions as in example I, part 3, usingthe sequence B-A. As a control, in one run the treatment with solution Bwas omitted.

Tests were carried out to determine the shrinkage characteristics of thetreated samples and also their permanence to extraction (with benzene, 3hours). The results are tabulated below:

' n.d.= not determined It was observed that the products in accordancewith the invention had a fuller, softer hand than the original(untreated) fabric.

EXAMPLE XlX Component A was a polyurethane prepared by reacting apolyether containing hydroxy groups with excess toluene diisocyanate toyield a polymer containing free isocyanate groups (average, more than 2per molecule). Viscosity of the polyurethane was 1,600 centipoises at 40C.,220 centipoises at 75 C. and contained 3.2 to 3.6 percent freeisocyanate.

Solution A: 3 percent of the polyurethane in methyl chloroform.

Solution B: 0.5 percent hexamethylene diamine (or ethylene diamine), 0.1percent wetting agent (isooctylphenyl ether of polyethylene glycol) inwater.

Wool cloth was treated with the solutions as described in example part3, using the sequence B-A. Shrinkage tests of the products are givenbelow:

it: Area shrinkage, cumulative in successive 75-minute washes inautomatic home washing machine. as described above.

EXAMPLE XX Solution A: A polyoxypropylene triol (average molecularweight 1,500; average hydroxyl No. 112) was dissolved in acetone atvarious concentrations as given below:

Solution B: 3 percent by volume of toluene diisocyanate in benzene.

Wool cloth was treated as described in example I, part 3, using thesequence AB and the cloth was air-dried after removal from solution Aand prior to entering into solution B.

The products, and a control sample in which the treatment with SolutionB was omitted, were tested for shrinkage before and after extractionwith acetone for 3'); hours in a Soxhlet extractor. The results aregiven below:

Shflnkw, Wool swatches were wet-out in solution A for various times C nof l wt nvrrnnt (as given below), passed through a squeeze roll, andair-dried i ig gflfi 1E 1d,,- at room temperature for one hour to removesolvent. The Procedur triol in Sal fabric: vxt racex n dried swatcheswere then dipped in solution B at room tem- 1 c De can perm 5 peraturefor one minute, passed through a squeeze roll, hand 4 4 411 washed andair-dried. Shrinkage tests on the products and a In accordance with 2 25. 9 N.d.

invention 1 1 M Na control sample (whereon the treatment with solution Bwas (15 Nvd om ted were for shr' ka e. The r lts are ive Control(Treated with tested m g esu g n $01. A only 4 4 18.1 23.4 be Blank(Untreated) 27 10 NOTE.N.d.=not determined. 7 w l I h firca t. p0ymmersion s rin age EMBODIMENT 4 amide in time in (Acceler- Sol. A, Sol.A, otor), per- In accordance with this embodiment of the inventlon, com-Run Procedure percent (500.) cent ponent A is a polyamide. Typ calexamples of such polymers 1 H In accordance with are given above in thesection entitled Component A- invention. 10 no 0 Polyamides. Especiallypreferred are the polyamides con- ,2 taining free primary or secondaryamino groups. A useful class 1. as on 0 of such polymers may beprepared, in known manner, by 3:2 reacting an aliphatic polyamine suchas one of the formula 0. 20 n f 0.125 20 n IINRNH H U Control (Notreatment in 10 60 22 V s01. B). (wherein R is a short chain alkyleneFadical such as CH 10 Blank (Untreated) Cl-l and n is 2 to 4) withheat-dimerized, unsaturated, high molecular weight fatty acids. Thepolyamides of this type are readily emulsifiable in water and may beapplied to the fibrous substrate in such form. In this event, componentB is preferably applied in solution in an essentially water-immiscible,organic solvent such as benzene, toluene, or the like. Since the highlyreactive groups of the preferred class of polyamides are primary orsecondary amino groups, component B is selected to contain complementaryreactive groups, e.g., carbonyl halide, sulphonyl halide, haloformate,carbamyl halide, anhydride, or isocyanate. Suitable compounds of thesetypes are given above in the sections listing the various types ofcomponent B. Generally, compounds containing isocyanate groups arepreferred as they not only form the cross-links rapidly but cause noevolution of acid byproducts (as is the case with acid halidefixatives).

Another useful plan for applying the aforesaid polyamides containingfree amino groups involves applying the polyamide to the substrate as asolution in a hydroxylated organic solvent such as ethanol orisopropanol (in which they are easily soluble). The treated substrate isthen dried to remove the solvent and the substrate then treated with theisocyanate-containing fixative dissolved in a solvent such as benzene ortoluene, thus to accomplish the cross-linking at a solid-liquidboundary.

This embodiment 4 of the invention is further illustrated below:

EXAMPLE XXI wherein represents the acyl radical of the dimerized fatacid and n is the number of repeating units, usually about 20 to 60 Thepolyamide had an amine value of 290-320( amine value is the milligramsequivalent of KOH per gram of polyamide) and a viscosity in a Brookfieldviscometer at 40 C. of 80-120 poises.

Solution A: The above polyamide in isopropanol at various concentrationsgiven below.

Solution B: Toluene diisocyanate (4 percent by volume) in benzene.

The products of run 1 in accordance with the invention and the control(run 9) were subjected to shrinkage tests before and after extractionwith isopropanol for 5 hours in a Soxhlet extraction. The results aregiven below:

Solution A: The polyamide of example XXI was dissolved in isopropanol inconcentration of 20 percent. One volume of this solution was poured into5 volumes of water containing ca. 0.0] percent of nonionic wettingagent, applying vigorous agitation to form an emulsion. This emulsionwas further diluted to various concentrations as given below.

Solution B: 2 percent toluene diisocyanate in methyl chloroform.

Samples of wool cloth and wool top (wool top is a thick but very openand loosely assembled strand of wool fibers with no twist) were treatedwith the solutions as described in example I, part 3, using the sequenceA-B. Tests for shrinkage of the products are tabulated below:

Wool top was treated with solutions of various complementary componentsA and B, using the technique described in example l, part 3. Theproducts were tested for shrinkage in the following manner: The productswere gilled to remove any fiber-to-fiber bonding which may have occurredduring treatment. The products were then cut to standard length (50 cm.sewn into a casing of cheesecloth, and given a 15-minute wash in anagitator-type household washing machine. After washing and air-drying,the samples were measured to determine the percentage of shrinkage. Thecomponents used and the results of the tests are tabulated below:

PA polyamide as described in Ex. XXI, in isopropanol.

PU polyurethane as described in Ex. XIX, in methyl chloroform.

Ter terpolymer of ethylene, vinyl acetate, and methacrylyl chloride asdescribed in Ex. I, in methyl chloroform.

TDI toluene diisocyanate in methyl chloroform.

HMDA hexamethylene diamine, in water plus 0.05%

nonionic wetting agent.

EMBODIMENT In accordance with this embodiment, component A is apolysiloxane. A particular benefit achieved with such copolymers is theimparting to the fibers of a high degree of water repellency andconsequently resistance to soils. Generally, the polysiloxane willcontain hydroxy or amine radicals as the highly reactive groups and thepolymer is preferably applied as a solution (or emulsion) in water.Component B is a compound containing carbonyl halide, sulphonyl halide,haloformate, carbamyl halide, anhydride, or isocyanate groups (thelatter being preferred) and is applied as a solution in an essentiallywater-immiscible solvent such as benzene, toluene, or the like.

This embodiment 5 of the invention is further illustrated below:

EXAMPLE XXIV Component A was a commercial polysiloxane containing morethan three amino groups per molecule. This polymer had a specificgravity of 0.988 to 1.005 at 25 C., viscosity 100 to 400 centistokes andcontained 5.5 to 6.3 percent free NH The repeating unit of thepolysiloxane is believed to have the Solution A: The above polysiloxanewas stirred into water containing added acetic acid to give a pH ofabout 1 l in the resulting milky solution. One solution at aconcentration of 3 percent polysiloxane and another at 1.5 percentpolysiloxane were thus prepared.

Solution B: 2 percent (by volume) of 2,4-toluene diisocyanate in methylchloroform.

Wool cloth was treated with the above solutions as in example 1, part 3,using the sequence A-B.

The results of tests on the products are given below:

\vttill repellency Ami V shrinkngi- Cone. of Wt. of After(Atltltl'tiitll'. polyslloxano resin on Brion After Accvlutter ox inSol. A, cloth, oxtracoxtrnc- (rotor traction). percent percent Lion tionwash port-out.

3 .2 lOO 3. ll 1.5 0. 5 80 100 100 T. 8 Control (Untreated). 0 50 37. U

Extract-ion with benzene, 3 hours in Soxhlut extractor.

No'rn lncrease in water repellency after cxtrnclinn and utter washingbelieved due to removal of nurcnctivi hydrophiliu. material from cloth.

Having thus described our invention, we claim: 1. Fibrous materialcarrying a deposit of a preformed polymer cross-linked in situ throughreaction with a fixative,

said preformed polymer being an addition polymerization product of atleast one polymerizable monomer containmg a grouping, said polymerhaving a molecular weight of at least 1 ,000 and containing :1haloformate groups,

said fixative being a polyamine containing m amino groups, n and m eachhaving a value of at least 2, the sum of n and m being at least 5. 2.The product of claim I wherein the preformed polymer is a copolymer of(i) a polymerizable monomer containing a grouping and a haloformategroup, and (ii) at least one other polymerizable monomer containing agrouping which is free from groups reactive with radicals containingactive hydrogen atoms.

3. Fibrous material carrying a deposit of a preformed polymercross-linked in situ through reaction with a fixative,

said preformed polymer being an addition polymerization product of atleast one polymerizable monomer containmg a grouping, said polymerhaving a molecular weight of at least 1 ,000 and containing 1:isocyanate groups,

said fixative being a polyamine containing m amino groups, n and m eachhaving a value of at least 2, the sum ofn and m being at least 5. 4. Theproduct of claim 3 wherein the preformed polymer is a copolymer of i) apolymerizable monomer containing a CHz C grouping and an isocyanategroup, and (ii) at least one other polymerizable monomer containing agrouping which is free from groups reactive with radicals containingactive hydrogen atoms.

5. Fibrous material carrying a deposit of a preformed polymercross-linked in situ through reaction with a fixative,

said preformed polymer being an addition polymerization product of atleast one polymerizable monomer containmg a grouping, said polymerhaving a molecular weight of at least 1,000 and containing n isocyanategroups,

said fixative being a polyol containing m hydroxy groups, n and m eachhaving a value of at least 2, the sum of n and m being at least 5. 6.The product of claim wherein the preformed polymer is a copolymer of (i)a polymerizable monomer containing a grouping and an isocyanate group,and (ii) at least one other polymerizable monomer containing a groupingwhich is free from groups reactive with radicals containing activehydrogen atoms.

7. Fibrous material carrying a deposit of a preformed polymercross-linked in situ through reaction with a fixative,

said preformed polymer being an addition polymerization product of atleast one polymerizable monomer containmg a grouping, said polymerhaving a molecular weight of at least 1,000 and containing n anhydridegroups,

said fixative being a polyamine containing m amino groups, n and m eachhaving a value of at least 2, the sum of n and m being at least 5. 8.The product of claim 7 wherein the preformed polymer is a copolymer of(i) a polymerizable monomer containing a grouping and an anhydridegroJand (ii) at least one other polymerizable monomer containing a groupingwhich is free from groups reactive with radicals containing activehydrogen atoms.

9. Fibrous material carrying a deposit of a preformed polymercross-linked in situ through reaction with a fixative,

said preformed polymer being an addition polymerization product of atleast one polymerizable monomer containmg a grouping, said polymerhaving a molecular weight of at least l,000 and containing 11 carbamylhalide groups,

said fixative being a polyamine containing m amino groups, n and m eachhaving a value of at least 2, the sum of n and m being at least 5. 10.The product of claim 9 wherein the preformed polymer is a copolymer of(i) a polymerizable monomer containing a grouping and a carbamyl halidegroup, and (ii) at least one other polymerizable monomer containing agrouping which is free from groups reactive with radicals con tainingactive hydrogen atoms.

11. Fibrous material carrying a deposit of a preformed polymercross-linked in situ through reaction with a fixative,

said preformed polymer being an addition polymerization product of atleast one polymerizable monomer containmg a grouping and an amino group,said polymer having a molecular weight of at least 1,000 and containingn amino groups,

said fixative containing m groups reactive with radicals containingactive hydrogen atoms, n and m each having a value of at least 2, thesum of n and m being at least 5. 12. The product of claim 11 wherein thefixative is a multifunctional isocyanate.

13. The product of claim 12 wherein the preformed polymer is a copolymerof (i) a polymerizable monomer containing a grouping and an amino group,and (ii) at least one other polymerizable monomer containing a groupingwhich is free from groups reactive with radicals containing activehydrogen atoms.

14. Fibrous material carrying a deposit of a preformed polymercross-linked in situ through reaction with a fixative,

said preformed polymer being an addition polymerization product of atleast one polymerizable monomer containmg a grouping, and a hydroxylgroup said polymer having a molecular weight of at least I ,000 andcontaining n hydroxyl groups,

said fixative containing m groups reactive with radicals containingactive hydrogen atoms, n and m each having a value of at least 2, thesum of n and m being at least 5. 15. The product of claim 14 wherein thefixative is a multifunctional isocyanate.

16. The product ,of claim 15 wherein the preformed polymer is acopolymer of (i) a polymerizable monomer containing a CII1:C

grouping and a hydroxyl group, and (ii) at least one other polymerizablemonomer containing a grouping which is free from groups reactive withradicals containing active hydrogen atoms.

17. Fibrous material carrying a deposit of a preformed condensationpolymer cross-linked in situ through reaction with a fixative,

said preformed condensation polymer being a polyester having a molecularweight of at least l,000 and containing n carbonyl halide groups,

said fixative being a polyamine containing m amino groups,

n and m each having a value of at least 2, the sum of n and m being atleast 5.

l8. Fibrous material carrying a deposit of a preformed condensationpolymer cross-linked in situ through reaction with a fixative,

said preformed condensation polymer being a polyester having a molecularweight of at least 1,000 and containing n haloformate groups,

said fixative being a polyamine containing m amino groups,

n and m each having a value of at least 2, the sum of n and m being atleast 5.

l9. Fibrous material carrying a deposit of a prefonned condensationpolymer cross-linked in situ through reaction with a fixative,

said preformed condensation polymer being a polyether having a molecularweight of at least l,000 and containing n carbonyl halide groups,

2. The product of claim 1 wherein the preformed polymer is a copolymerof (i) a polymerizable monomer containing a grouping and a haloformategroup, and (ii) at least one other polymerizable monomer containing agrouping which is free from groups reactive with radicals containingactive hydrogen atoms.
 3. Fibrous material carrying a deposit of apreformed polymer cross-linked in situ through reaction with a fixative,said preformed polymer being an addition polymerization product of atleast one polymerizable monomer containing a grouping, said polymerhaving a molecular weight of at least 1, 000 and containing n isocyanategroups, said fixative being a polyamine containing m amino groups, n andm each having a value of at least 2, the sum of n and m being at least5.
 4. The product of claim 3 wherein the preformed polymer is acopolymer of (i) a polymerizable monomer containing a grouping and anisocyanate group, and (ii) at least one other polymerizable monomercontaining a grouping which is free from groups reactive with radicalscontaining active hydrogen atoms.
 5. Fibrous material carrying a depositof a preformed polymer cross-linked in situ through reaction with afixative, said preformed polymer being an addition polymerizationproduct of at least one polymerizable monomer containing a grouping,said polymer having a molecular weight of at least 1, 000 and containingn isocyanate groups, said fixative being a polyol containing m hydroxygroups, n and m each having a value of at least 2, the sum of n and mbeing at least
 5. 6. The product of claim 5 wherein the preformedpolymer is a copolymer of (i) a polymerizable monomer containing agrouping and an isocyanate group, and (ii) at least one otherpolymerizable monomer containing a grouping which is free from groupsreactive with radicals containing active hydrogen atoms.
 7. Fibrousmaterial carrying a deposit of a preformed polymer cross-linked in situthrough reaction with a fixative, said preformed polymer being anaddition polymerization product of at least one polymerizable monomercontaining a grouping, said polymer having a molecular weight of atleast 1, 000 and containing n anhydride groups, said fixative being apolyamine containing m amino groups, n and m each having a value of atleast 2, the sum of n and m being at least
 5. 8. The product of claim 7wherein the preformed polymer is a copolymer of (i) a polymerizablemonomer containing a grouping and an anhydride group, and (ii) at leastone other polymerizable monomer containing a grouping which is free fromgroups reactive with radicals containing active hydrogen atoms. 9.Fibrous material carrying a deposit of a preformed polymer cross-linkedin situ through reaction with a fixative, said preformed polymer beingan addition polymerization product of at least one polymerizable monomercontaining a grouping, said polymer having a molecular weight of atleast 1, 000 and containing n carbamyl halide groups, said fixativebeing a polyamine containing m amino groups, n and m each having a valueof at least 2, the sum of n and m being at least
 5. 10. The product ofclaim 9 wherein the preformed polymer is a copolymer of (i) apolymerizable monomer containing a grouping and a carbamyl halide group,and (ii) at least one other polymerizable monomer containing a groupingwhich is free from groups reactive with radicals containing activehydrogen atoms.
 11. Fibrous material carrying a deposit of a preformedpolymer cross-linked in situ through reaction with a fixative, saidpreformed polymer being an addition polymerization product of at leastone polymerizable monomer containing a grouping and an amino group, saidpolymer having a molecular weight of at least 1,000 and containing namino groups, said fixative containing m groups reactive with radicalscontaining active hydrogen atoms, n and m each having a value of atleast 2, the sum of n and m being at least
 5. 12. The product of claim11 wherein the fixative is a multifunctional isocyanate.
 13. The productof claim 12 wherein the preformed polymer is a copolymer of (i) apolymerizable monomer containing a grouping and an amino group, and (ii)at least one other polymerizable monomer containing a grouping which isfree from groups reactive with radicals containing active hydrogenatoms.
 14. Fibrous material carrying a deposit of a preformed polymercross-linked in situ through reaction with a fixative, said preformedpolymer being an addition polymerization product of at least onepolymerizable monomer containing a grouping, and a hydroxyl group saidpolymer having a molecular weight of at least 1,000 and containing nhydroxyl groups, said fixative containing m groups reactive withradicals containing active hydrogen atoms, n and m each having a valueof at least 2, the sum of n and m being at least
 5. 15. The product ofclaim 14 wherein the fixative is a multifunctional isocyanate.
 16. Theproduct of claim 15 wherein the preformed polymer is a copolymer of (i)a polymerizable monomer containing a grouping and a hydroxyl group, and(ii) at least one other polymerizable monomer containing a groupingwhich is free from groups reactive with radicals containing activehydrogen atoms.
 17. Fibrous material carrying a deposit of a preformedcondensation polymer cross-linked in situ through reaction with afixative, said preformed condensation polymer being a polyester having amolecular weight of at least 1,000 and containing n carbonyl halidegroups, said fixative being a polyamine containing m amino groups, n andm each having a value of at least 2, the sum of n and m being at least5.
 18. Fibrous material carrying a deposit of a preformed condensationpolymer cross-linked in situ through reaction with a fixative, saidpreformed condensation polymer being a polyester having a molecularweight of at least 1,000 and containing n haloformate groups, saidfixative being a polyamine containing m amino groups, n and m eachhaving a value of at least 2, the sum of n and m being at least
 5. 19.Fibrous material carrying a deposit of a preformed condensation polymercross-linked in situ through reaction with a fixative, said preformedcondensation polymer being a polyether having a molecular weight of atleast 1,000 and containing n carbonyl halide groups, said fixative beinga polyamine containing m amino groups, n aNd m each having a value of atleast 2, the sum of n and m being at least
 5. 20. Fibrous materialcarrying a deposit of a preformed condensation polymer cross-linked insitu through reaction with a fixative, said preformed condensationpolymer being a polyether having a molecular weight of at least 1,000and containing n haloformate groups, said fixative being a polyaminecontaining m amino groups, n and m each having a value of 2, the sum ofn and m being at least
 5. 21. Fibrous material carrying a deposit of apreformed condensation polymer cross-linked in situ through reactionwith a fixative, said preformed condensation polymer being a polyglycolpolyether having a molecular weight of at least 1,000 and containing nhydroxyl groups, said fixative being a polyisocyanate containing misocyanate groups, n and m each having a value of at least 2, the sum ofn and m being at least
 5. 22. The product of claim 21 wherein thepreformed polyglycol polyether is a polymerization product of a loweralkylene oxide and an aliphatic polyol.
 23. A process for modifying afibrous material which comprises impregnating a fibrous material with asolution of a reactant in a volatile solvent, drying the treated fibrousmaterial to remove the volatile solvent, and impregnating the driedfibrous material with a complementary reactant in a fluid state, one ofsaid reactants being a preformed polymer having a molecular weight of atleast 1,000 and bearing n carbonyl halide groups, the other of saidreactants being a fixative bearing m amino groups, n and m each having avalue of at least 2, the sum of n and m being at least 5, the saidpolymer directly cross-linking with the fixative under said conditionsto form a three-dimensional structure on the fibrous material.
 24. Aprocess for modifying a fibrous material which comprises impregnating afibrous material with a solution of a reactant in a volatile solvent,drying the treated fibrous material to remove the volatile solvent, andimpregnating the dried fibrous material with a complementary reactant ina fluid state, one of said reactants being a preformed polymer having amolecular weight of at least 1,000 and bearing n haloformate groups, theother of said reactants being a fixative bearing m amino groups, n and meach having a value of at least 2, the sum of n and m being at least 5,the said polymer directly cross-linking with the fixative under saidconditions to form a three-dimensional structure on the fibrousmaterial.
 25. A process for modifying a fibrous material which comprisesimpregnating a fibrous material with a solution of a reactant in avolatile solvent, drying the treated fibrous material to remove thevolatile solvent, and impregnating the dried fibrous material with acomplementary reactant in a fluid state, one of said reactants being apreformed polymer having a molecular weight of at least 1,000 andbearing n anhydride groups, the other of said reactants being a fixativebearing m amino groups, n and m each having a value of at least 2, thesum of n and m being at least 5, the said polymer directly cross-linkingwith the fixative under said conditions to form a three-dimensionalstructure on the fibrous material.
 26. A process for modifying a fibrousmaterial which comprises impregnated a fibrous material with a solutionof a reactant in a volatile solvent, drying the treated fibrous materialto remove the volatile solvent, and impregnating the dried fibrousmaterial with a complementary reactant in a fluid state, one of saidreactants being a preformed Polymer having a molecular weight of atleast 1,000 and bearing n amino groups, the other of said reactantsbeing a fixative bearing m carbonyl halide groups, n and m each having avalue of at least 2, the sum of n and m being at least 5, the saidpolymer directly cross-linking with the fixative under said conditionsto form a three-dimensional structure on the fibrous material.
 27. Aprocess for modifying a fibrous material which comprises impregnating afibrous material with a solution of a reactant in a volatile solvent,drying the treated fibrous material to remove the volatile solvent, andimpregnating the dried fibrous material with a complementary reactant ina fluid state, one of said reactants being a preformed polymer having amolecular weight of at least 1,000 and bearing n amino groups, the otherof said reactants being a fixative bearing m haloformate groups, n and meach having a value of at least 2, the sum of n and m being at least 5,the said polymer directly cross-linking with the fixative under saidconditions to form a three-dimensional structure on the fibrousmaterial.
 28. A process for modifying a fibrous material which comprisesimpregnating a fibrous material with a solution of a reactant in avolatile solvent, drying the treated fibrous material to remove thevolatile solvent, and impregnating the dried fibrous material with acomplementary reactant in a fluid state, one of said reactants being apreformed polymer having a molecular weight of at least 1,000 andbearing n amino groups, the other of said reactants being a fixativebearing m anhydride groups, n and m each having a value of at least 2,the sum of n and m being at least 5, the said polymer directlycross-linking with the fixative under said conditions to form athree-dimensional structure on the fibrous material.